Supporting Information for

0 downloads 0 Views 1MB Size Report
hexane (10.4 mmol, 1.2 eq.), 10.4 mL of a 1.0 m solution of Catecholborane in diethylether. (10.4 mmol, 1.2 eq.) were added dropwise and the solution stirred at ...

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

Supporting Information for: Tunneling Control in Chemical Reactions: C–H Insertion versus H-Tunneling in tert.-butylhydroxycarbene David Ley, Dennis Gerbig, and Peter R. Schreiner * Justus-Liebig-University, Heinrich-Buff-Ring 58, 35392 Giessen, Germany

Table of contents 1)

Synthetical details ..................................................................................................................................S2 fig. S1: Synthesis scheme .................................................................................................................S2 a) Isobutylene ............................................................................................................................S2 b) 1,1-Dimethyl-2.2-dibromocyclopropane ................................................................................S2 c) 1,1-Dimethylcyclopropane-2-ol..............................................................................................S2

2)

Matrix isolation spectra .........................................................................................................................S3 fig. S2: Matrix-isolated 13 ..................................................................................................................S3 fig. S3: Pyrolysis of 13 .......................................................................................................................S4 fig. S4: Matrix-isolated d-13...............................................................................................................S4 fig. S5: Pyrolysis of d-13....................................................................................................................S5 fig. S6: Matrix-isolated 10 ..................................................................................................................S5 fig. S7: Matrix-isolated 11 ..................................................................................................................S6 fig. S8: Pyrolysis of 11 .......................................................................................................................S6 fig. S9: Matrix-isolated 17 ..................................................................................................................S7 fig. S10: Matrix-isolated 14 ..................................................................................................................S7 fig. S11: Matrix-isolated 16 ..................................................................................................................S8

3)

Kinetic plots and half-life evaluation ...................................................................................................S8 a) Half-life overview ...................................................................................................................S8 b) IR measurements at 11 K......................................................................................................S9 c) IR measurements at 20 K....................................................................................................S14 d) Aldehyde increase via tunneling..........................................................................................S19

4)

Geometries and high level energies ...................................................................................................S20 a) Scheme 2: M06-2X/6-311++G(d,p) .....................................................................................S20 b) Scheme 3: CCSD(T)/cc-pVDZ,fc.........................................................................................S24 c) Scheme 3: M06-2X/6-311++G(d,p) .....................................................................................S29 d) Scheme 5: M06-2X/6-311++G(d,p) .....................................................................................S35

5)

Crystal data and structure refinement for the dimer of 13................................................................S42

6)

Full references for electronic structure codes...................................................................................S44 a) Gaussian09 .........................................................................................................................S44 b) CFOUR................................................................................................................................S44 c) ORCA ..................................................................................................................................S44

S1  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

1) Synthetical details

Figure S1: Scheme for the synthesis of dimethylcyclopropanol (11), based on isobutylene (14), which is readily accessible via H2SO4-catalyzed dehydration of tert.-butanol. a) Isobutylene (14) In a 250 mL round-bottom flask with a reflux condensor (cooled with water to approx. 20 °C) and a superimposed distillation bridge (cooled with ethanol to approx. –25 °C),

the mixture of 150 g

(2.0 mol) tert.-Butanol and 10 g (0.1 mol) was heated under gentle reflux after the apparatus was purged with Argon. Approx. 100 g (1.8 mol) Isobutylene (b.p. –6.9 °C) were obtained and stored in the freezer at –18 °C. c)

1,1-Dimethyl-2,2-dibromocyclopropane

In a 250 mL round-bottom flask, to 12.6 g (0.05 mol) CHBr3 were added 20 mL dichloromethane, 2 mL ethanol, and 116 mg (0.5 mmol) Benzyltriethylammonium chloride and the stirred solution was cooled to –6 °C, followed by the dropwise addition of 15 g (0.27 mol) Isobutylene.

During the dropwise

addition of 20 mL aq. NaOH (42 %) the reaction mixture warmed up to +2 °C and after the addition was complete, the reaction mixture was stirred for 5 h at +8 °C. 90 mL H2O were added to the vigorously stirred reaction mixture and the phases were separated. The aqueous layer was extracted three times, each with 30 mL CH2Cl2, the combined organic layers were washed with 15 mL 15 % HCl and dried over Na2SO4. The solvent was distilled of and the crude product was distilled in vacuo; yield: 8.12 g (36 mmol) 1,1-Dimethyl-2,2-dibromocyclopropane (72 %); b.p. 51 °C/30 mbar.

1

H-NMR (CDCl3): δ = 1.38 (s, 2 CH2); δ = 1.34 (s, 6 CH3).

13

C-NMR (400 MHz,

CDCl3): δ = 39.75 (CBr2); δ = 35.04 (CH2); δ = 26.39 (C(CH3)2); δ = 25.30 ((CH3)2). d) 1,1-Dimethyl-cyclopropane-2-ol In a 100 mL two-neck round bottom flask (under Argon, after thoroughly drying by heating under vacuum), the stirred solution of 1.99 g (8.7 mmol) 1,1-Dimethyl-2,2-dibromocyclopropane in 35 mL of dry THF was cooled to –90 °C. After the dropwise addition of 6.5 mL 1.6 m solution of n-BuLi in

S2  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

hexane (10.4 mmol, 1.2 eq.), 10.4 mL of a 1.0 m solution of Catecholborane in diethylether (10.4 mmol, 1.2 eq.) were added dropwise and the solution stirred at –90 °C for 1 h. After the reaction mixture was allowed to warm up to room temperature, the solvent was distilled of under Ar and the white residue was finally dissolved in CH2Cl2/THF. To the organic solution was added the solution of 4.8 g (0.12 mol) in 25 mL H2O, followed by 25 mL of a 30 % H2O2 solution and the red reaction mixture was vigorously stirred. The organic layer was separated and the aqueous layer was extracted three times, each with 25 mL Diethylether.

The combined organic layers were dried over Na2SO4, the

solvent was distilled of in vacuo. The residue (crude product) was purified by means of preparative gas chromatography; yield: 280 mg (3.3 mmol) 1,1-Dimethylcyclopropane-2-ol (37 %).

1

H-NMR

(400 MHz, CDCl3): δ = 3.22 (m, 1 CH); δ = 2.21 (s, 1 OH); δ = 1.61 (s, 3 CH3); δ = 1.10 (s, 3 CH3); δ = 0.47 (m, 1 CH2); δ = 0.29 (m, 1 CH2).

13

C-NMR (400 MHz, CDCl3): δ = 57.01 (COH); δ = 24.40 (CH3);

δ = 21.21 (C(CH3)2); δ = 18.20 (CH2).

2) Matrix isolation spectra

  Figure S2: Matrix-isolated tert.-butylglyoxylic acid (13) in Ar at 11 K.

S3  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

  Figure S3: Matrix-isolated products of the pyrolysis (960 °C) of tert.-butylglyoxylic acid (13) in Ar at 11 K.

  Figure S4: Matrix-isolated O-deuterated tert.-butylglyoxylic acid (d-13) in Ar at 11 K.  

S4  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

 

  Figure S5: Matrix-isolated products of the pyrolysis (960 °C) of O-deuterated tert.-butylglyoxylic acid (d13) in Ar at 11 K.

   

  Figure S6: Matrix-isolated pivaldehyde (10) in Ar at 11 K.

S5  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

  Figure S7: Matrix-isolated 1,1-Dimethyl-propane-2-ol (11) in Ar at 11 K.

     

  Figure S8: Matrix-isolated products of the pyrolysis (960 °C) of 1,1-Dimethylcyclopropane-2-ol (11) in Ar at 11 K.

S6  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

  Figure S9: Matrix-isolated Isopropyl-methyl ketone (17) in Ar at 11 K.

  Figure S10: Matrix-isolated Isobutylene (14) in Ar at 11 K.

S7  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

  Figure S11: Matrix-isolated Formaldehyde (16) in Ar at 11 K.

3) Kinetic plots and half-life evaluation a) Half-life overview Based on a first order decay mechanism, the half-life of 9 was determined at different temperatures. For this purpose, the height of the IR absorbance of a decaying signal was monitored over time while carefully shielding the matrix from external light. The absorbance A0 after complete decay was subtracted from A, and the obtained absorbance difference ΔA was normalized through dividing by A0. The logarithm of this quotient ln(ΔA/A0) was then plotted against t to obtain the first-order decay constant k. The ordinate value will eventually go to 0 in the long time limit, but this is not apparent from our plots: As the relative change decreases with ongoing time, we could only reliably monitor the decaying signal for a time period which is 4 in the range of 10 s. The half-life τ equals ln(2)/abs(k). The half-life was determined for the five strongest signals of 9 and was averaged, disregarding the least reliable values (based on the IR spectrum).

Table S1: Array of all single half-lives measured at 11 K and 20 K. Average half-lives were determined to be (1.7 ± 0.2) h at 11 K and (1.7 ± 0.2) h at 20 K.

ν [cm –1] T [K]

τ [h] 11 20

3546 (0.5 ± 4.0) (2.7 ± 0.3)

1297 1.8 ± 0.1 1.8 ± 0.1

1296 1.7 ± 0.1 1.6 ± 0.1

1183 (1.3 ± 0.2) 1.7 ± 0.1

780 1.5 ± 0.3 (1.0 ± 0.3) S8

 

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

b)

IR measurements at 11 K

  –1

Figure S12: First-order kinetics plot for the evaluation of k at 11 K (780 cm ) for the disappearance of 9 over time.

–1

Table S2: Kinetic data for the evaluation of k at 11 K (780 cm ) for the disappearance of 9 over time.

t/s 0 929 2167 4580 8495 13755 ∞

A 0.0238891 0.0236729 0.0233036

ln[(A–A0)/A0] –2.8259546 –3.0024412 –3.4024752

0.0229822

–3.4024752

0.0225528

--

S9  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

  –1

Figure S13: First-order kinetics plot for the evaluation of k at 11 K (1183 cm ) for the disappearance of 9 over time.

–1

Table S3: Kinetic data for the evaluation of k at 11 K (118a3 cm ) for the disappearance of 9 over time.

t/s 0 929 2167 4580 8495 13755 ∞

A 0.048561 0.048259 0.047657 0.047262 0.046848 0.046359 0.046076

ln[(A–A0)/A0] –2.92001954 –3.04959212 –3.37223464 –3.65970590 –4.08906293 –5.09260058 --

S10  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

  –1

Figure S14: First-order kinetics plot for the evaluation of k at 11 K (1296 cm ) for the disappearance of 9 over time.

        –1

Table S4: Kinetic data for the evaluation of k at 11 K (1296 cm ) for the disappearance of 9 over time.

t/s 0 929 2167 4580 8495 13755 ∞

A 0.088699 0.088157 0.087463 0.086117 0.084673 0.083507 0.082022

ln[(A–A0)/A0] –2.50831871 –2.59297742 –2.71302463 –2.99722078 –3.43205057 –4.01157273 --

S11  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

  –1

Figure S15: First-order kinetics plot for the evaluation of k at 11 K (1297 cm ) for the disappearance of 9 over time.

        –1

Table S5: Kinetic data for the evaluation of k at 11 K (1297 cm ) for the disappearance of 9 over time.

t/s 0 929 2167 4580 8495 13755 ∞

A 0.088768 0.08788 0.087172 0.085895 0.084534 0.083396 0.081772

ln[(A–A0)/A0] –2.45859633 –2.59433549 –2.71753593 –2.98735383 –3.38797983 –3.91904264 --

S12  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

  –1

Figure S16: First-order kinetics plot for the evaluation of k at 11 K (3546 cm ) for the disappearance of 9 over time.

        –1

Table S6: Kinetic data for the evaluation of k at 11 K (3546 cm ) for the disappearance of 9 over time.

t/s 0 929 2167 4580 8495 13755 ∞

A 0.3315863 0.3314794 0.3307245 0.3303577

ln[(A–A0)/A0] -5.373142259 -5.445508635 -6.200483421 -6.99427237

0.081772

--

S13  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

c)

IR measurements at 20 K

  –1

Figure S17: First-order kinetics plot for the evaluation of k at 20 K (780 cm ) for the disappearance of 9 over time.

        –1

Table S7: Kinetic data for the evaluation of k at 20 K (780 cm ) for the disappearance of 9 over time.

t/s

A

0 1068 2406 3582 4446 5348 8595 ∞

0.9880552 0.9876295 0.9872674 0.987101 0.9869688 0.9866654 0.9864697 0.9860733

ln[(A–A0)/A0] –6.20967471 –6.45148374 –6.71633792 –6.86640739 –7.00410375 –7.41781043 –7.81906216 --

S14  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

  –1

Figure S18: First-order kinetics plot for the evaluation of k at 20 K (1183 cm ) for the disappearance of 9 over time.

        –1

Table S8: Kinetic data for the evaluation of k at 20 K (1183 cm ) for the disappearance of 9 over time.

t/s 0 1068 2406 3582 4446 5348 8595 ∞

A 0.037401 0.036981 0.036777 0.036574 0.036303 0.036004 0.035774 0.034621

ln[(A–A0)/A0] –2.55311761 –2.72212574 –2.81581514 –2.91866450 –3.07486281 –3.28130322 –3.47534969 --

S15  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

  –1

Figure S19: First-order kinetics plot for the evaluation of k at 20 K (1296 cm ) for the disappearance of 9 over time.

        –1

Table S9: Kinetic data for the evaluation of k at 20 K (1296 cm ) for the disappearance of 9 over time.

t/s 0 1068 2406 3582 4446 5348 8595 ∞

A 0.039845 0.039217 0.038632 0.038109 0.037659 0.037377 0.036562 0.0347

ln[(A–A0)/A0] –1.90871431 –2.03889163 –2.17759148 –2.32032069 –2.46188831 –2.56204292 –2.92508850 --

S16  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

  –1

Figure S20: First-order kinetics plot for the evaluation of k at 11 K (1297 cm ) for the disappearance of 9 over time.

        –1

Table S10: Kinetic data for the evaluation of k at 20 K (1297 cm ) for the disappearance of 9 over time.

t/s 0 1068 2406 3582 4446 5348 8595 ∞

A 0.048808 0.04827 0.047374 0.046967 0.046609 0.046286 0.045282 0.042797

ln[(A–A0)/A0] –1.96287688 –2.05664109 –2.23542424 –2.32855197 –2.41831402 –2.50685284 –2.84619534 --

S17  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

  –1

Figure S21: First-order kinetics plot for the evaluation of k at 11 K (3546 cm ) for the disappearance of 9 over time.

        –1

Table S11: Kinetic data for the evaluation of k at 20 K (3546 cm ) for the disappearance of 9 over time.

t/s 0 1068 2406 3582 4446 5348 8595 ∞

A 0.2526268 0.2523054 0.2518357 0.2514236 0.2512506 0.2510775 0.2507479 0.248325

ln[(A–A0)/A0] –4.05570483 –4.13335605 –4.25892292 –4.38378797 –4.44123878 –4.50222878 –4.62977320 --

S18  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

d)

Increase in the Aldehyde concentration due to tunneling

  Figure S22: Tunneling disappearance of 9 leads to an increase of the concentration of the corresponding –1 aldehyde (10), shown on its strongest band at 1733.8 cm .

S19  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

4) Geometries (in Å) and high-level energies (in a.u.) a) Scheme 2: M06-2X/6-311++G(d,p) 13 6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 6 8 8 1

-0.909399000 -0.094515000 -0.567394000 -0.567394000 -2.392796000 -0.567394000 0.474462000 -1.203363000 -0.769115000 0.474462000 -0.769115000 -1.203363000 -2.652938000 -2.991405000 -2.652938000 1.465417000 2.089918000 2.025014000 1.309493000

-0.649712000 0.626506000 -1.461962000 -1.461962000 -0.279504000 1.736858000 -1.779594000 -2.350131000 -0.882945000 -1.779594000 -0.882945000 -2.350131000 0.308262000 -1.192835000 0.308262000 0.552740000 -0.465310000 1.757256000 2.414581000

E[M06-2X] ZPVE[M06-2X] E[CCSD(T)]

= = =

6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 6 8 8 1

-0.293324000 0.387185000 -1.188637000 -1.188637000 0.646292000 1.674075000 -1.852229000 -1.795084000 -0.589391000 -1.852229000 -0.589391000 -1.795084000 1.289165000 0.063015000 1.289165000 0.008335000 -1.143940000 1.165977000 2.035897000

0.000000000 0.000000000 1.263168000 -1.263168000 0.000000000 0.000000000 1.267819000 1.286011000 2.168174000 -1.267819000 -2.168174000 -1.286011000 0.882128000 0.000000000 -0.882128000 0.000000000 0.000000000 0.000000000 0.000000000

–460.2895878 0.1577536 –459.163762776858

TS1 -1.325456000 0.014049000 -1.325456000 -1.325456000 -2.531977000 -0.085291000 -0.458624000 -2.234841000 -1.308607000 -0.458624000 -1.308607000 -2.234841000 -2.532266000 -3.456053000 -2.532266000 2.396404000 2.526315000 2.595243000 0.821939000

E[M06-2X] ZPVE[M06-2X] E[CCSD(T)]

= = =

0.000000000 0.000000000 1.253330000 -1.253330000 0.000000000 0.000000000 1.257185000 1.259688000 2.167013000 -1.257185000 -2.167013000 -1.259688000 0.882687000 0.000000000 -0.882687000 0.000000000 0.000000000 0.000000000 0.000000000

–460.2254706 0.1544489 –459.099202306152

S20  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

9 • CO2 6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 6 8 8 1

1.464731000 0.032450000 1.575030000 1.640172000 2.516793000 -0.014413000 0.809741000 2.560722000 1.449173000 0.896854000 1.550570000 2.636474000 2.369617000 3.516141000 2.473136000 -2.707834000 -2.758494000 -2.782402000 -0.948009000

-0.172113000 0.301819000 -1.336487000 -0.716104000 0.900048000 1.601991000 -2.088372000 -1.802269000 -0.988481000 -1.483603000 0.083530000 -1.156926000 1.332784000 0.458889000 1.711229000 -0.213764000 -1.364058000 0.947618000 1.868427000

E[M06-2X] ZPVE[M06-2X] E[CCSD(T)]

= = =

6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 1

0.010820000 -0.556192000 -1.144302000 0.253044000 1.276832000 -0.014251000 -2.057008000 -0.855886000 -1.353814000 -0.647461000 1.060607000 0.533910000 1.102791000 1.607325000 2.088073000 -0.405743000

-0.017403000 -0.043941000 -1.011033000 1.416550000 -0.310440000 -0.038089000 -0.808986000 -0.927971000 -2.039409000 1.640498000 2.156027000 1.506145000 -1.302849000 -0.275665000 0.418214000 -0.011577000 -0.008767000 -0.012516000 -0.023959000

–460.2265504 0.1547237 –459.102059050628

9 0.335066000 -0.901681000 0.819513000 1.373116000 0.121328000 -1.962220000 0.975623000 1.766996000 0.098458000 1.512000000 1.057457000 2.331293000 -0.576999000 1.073434000 -0.277950000 -2.746610000

E[M06-2X] ZPVE[M06-2X] E[CCSD(T)]

= = =

0.016511000 0.677701000 -0.885891000 1.119480000 -0.817730000 0.130934000 -0.307922000 -1.348766000 -1.679943000 1.720341000 1.784879000 0.673670000 -1.637914000 -1.240851000 -0.204062000 0.532675000

–271.6395447 0.1414336 –270.944400991784

S21  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

CO2 6 8 8

0.000000000 0.000000000 0.000000000

0.000000000 0.000000000 0.000000000

E[M06-2X] ZPVE[M06-2X] E[CCSD(T)]

= = =

6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 6 8 8 1

-0.177960000 0.748200000 -1.219289000 -0.856429000 0.691223000 1.794379000 -1.870530000 -1.852053000 -0.745983000 -1.483760000 -0.106130000 -1.483970000 1.186888000 0.063108000 1.456516000 -0.161210000 -0.990132000 0.431243000 0.804782000

0.000000000 1.154787000 -1.154787000

–188.5748797 0.011992 –188.146680429605

TS2 -1.110502000 0.086185000 -0.791555000 -1.410920000 -2.301506000 0.043958000 0.032997000 -1.665125000 -0.533511000 -0.578783000 -1.605357000 -2.299590000 -2.110666000 -3.188327000 -2.504399000 1.854536000 1.888364000 2.471509000 1.264689000

E[M06-2X] ZPVE[M06-2X] E[CCSD(T)]

= = =

6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 1

0.329519000 -1.085102000 1.026554000 1.026554000 0.312568000 -2.086718000 1.003282000 2.073310000 0.551825000 1.003282000 0.551825000 2.073310000 -0.206266000 1.334911000 -0.206266000 -1.146035000

0.113843000 -0.095684000 1.187085000 -1.233579000 0.537125000 -0.679088000 0.886003000 1.358058000 2.139193000 -1.557255000 -2.002497000 -1.128155000 1.492383000 0.649139000 -0.212925000 -0.035685000 -0.855586000 0.874963000 0.815123000

–460.1646941 0.1495502 –459.038837086659

10 -0.003639000 -0.551004000 -0.551004000 -0.551004000 1.520627000 0.109876000 -1.644206000 -0.237211000 -0.175907000 -1.644206000 -0.175907000 -0.237211000 1.903558000 1.906691000 1.903558000 -1.662036000

E[M06-2X] ZPVE[M06-2X]

= =

0.000000000 0.000000000 1.254386000 -1.254386000 0.000000000 0.000000000 1.278026000 1.260292000 2.164171000 -1.278026000 -2.164171000 -1.260292000 0.880700000 0.000000000 -0.880700000 0.000000000

–271.7211251 0.1413691

S22  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

E[CCSD(T)]

=

–271.029808536481

6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 6 8 8 1

0.097573000 -0.232333000 1.479972000 0.034433000 -0.999472000 -1.211303000 2.136667000 1.905487000 1.458309000 0.713505000 -0.977422000 0.339216000 -1.355954000 -0.852623000 -1.909263000 0.231361000 1.249884000 -0.511080000 -1.347128000

TS3 -1.761828000 0.542778000 -1.795227000 -1.790491000 -2.123392000 0.433059000 -1.063320000 -2.792660000 -1.609806000 -1.060050000 -1.606833000 -2.786675000 -0.695601000 -2.472259000 -2.443509000 1.959796000 2.344577000 2.728037000 2.295507000

E[M06-2X] ZPVE[M06-2X] E[CCSD(T)]

= = =

0.110976000 -0.178358000 -0.484732000 1.614302000 -0.644934000 -0.941286000 -0.013767000 -0.321460000 -1.559291000 2.054843000 1.978604000 1.956209000 -0.968890000 -1.663094000 -0.145590000 0.000841000 -0.487484000 0.821631000 1.030981000

–460.1509246 0.1496166 –459.018018759936

HO–C–COOH 6 8 1 6 8 8 1

-0.828263000 -1.729087000 -2.601094000 0.500301000 0.733256000 1.431087000 1.086818000

-0.443814000 -0.004409000 -0.314161000 0.129317000 1.298706000 -0.809359000 -1.678351000

E[M06-2X] ZPVE[M06-2X] E[CCSD(T)]

= = =

6 6 6 6 1 1 1 1 1 1 1 1

1.271323000 0.000000000 -1.271323000 0.000000000 0.925800000 -0.925800000 1.313363000 1.313363000 2.153372000 -1.313363000 -1.313363000 -2.153372000

0.516088000 -0.296100000 -0.013874000 0.065447000 0.028033000 -0.174930000 0.068643000

–302.9704847 0.0436289 –302.260439566187

14 0.000000000 0.000000000 0.000000000 0.000000000 0.000000000 0.000000000 -0.879049000 0.879049000 0.000000000 0.879049000 -0.879049000 0.000000000

E[M06-2X]

=

-0.678377000 0.125374000 -0.678377000 1.456251000 2.020849000 2.020849000 -1.328911000 -1.328911000 -0.037642000 -1.328911000 -1.328911000 -0.037642000

–157.180771

S23  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

ZPVE[M06-2X] E[CCSD(T)]

= =

0.1084038 –156.759592784376

b) Scheme 3: CCSD(T)/cc-pVDZ, fc 9 6 8 1 6 6 1 1 1 6 1 1 1 6 1 1 1

3

0.875136861 1.926649589 2.708559987 -0.397961559 -0.182931098 -1.158395399 0.338030145 0.425870399 -1.259904973 -0.779205022 -2.251755316 -1.405119396 -1.101387118 -0.504441880 -2.090283043 -1.248602530

-0.823701452 -0.025835756 -0.590250595 0.014809909 1.524304633 2.033721123 1.985046183 1.714992438 -0.229987947 0.200030572 0.248624305 -1.312856152 -0.616347501 -0.467646783 -0.139983025 -1.702775820

E[CCSD(T)] ZPVE[CCSD(T)]

= =

6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 1

-0.000852896 0.011473880 -1.256547925 -0.030639082 1.271233192 0.060764355 -2.181783372 -1.271464664 -1.259736266 -0.935433836 0.857105549 -0.034902235 1.325924142 1.259806001 2.180709090 -0.841101657

0.197074503 0.024753372 0.144682547 0.001460185 -0.221223994 -0.347204867 0.639305586 -1.124490859 1.261728861 2.162429730 1.140501773 1.432907531 -1.225506668 -2.146770296 -1.375387292 -1.079961551

–270.946643843804 87.9311 kcal/mol

9 -0.450677307 0.884612902 -0.522204630 -1.585351971 -0.558765232 2.087925791 -0.464982207 -1.473570262 0.312054543 -1.517117803 -1.537344106 -2.568940042 0.288918422 -1.503650057 -0.543515984 2.451890416

E[CCSD(T)] ZPVE[CCSD(T)]

= =

-0.015098147 -0.745342906 0.888350682 -1.055389243 0.860619322 -0.111736697 0.282746289 1.456492088 1.616431323 -1.689005855 -1.713951446 -0.546224832 1.569263024 1.440242155 0.230923193 -0.077479466

–270.901880494523 87.0198 kcal/mol

S24  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

TS4 6 8 1 6 6 1 1 1 6 1 1 1 6 1 1 1

0.893635924 2.010551097 2.063349535 -0.428989163 -0.178984558 -1.144946930 0.395828207 0.395828207 -1.201802348 -0.660811847 -2.199373716 -1.340307211 -1.201802348 -0.660811847 -2.199373716 -1.340307211

0.754151093 0.042364153 1.223477570 -0.014821270 -1.532351985 -2.072950059 -1.842138718 -1.842138718 0.424606829 0.130189198 -0.056225294 1.522204869 0.424606829 0.130189198 -0.056225294 1.522204869

E[CCSD(T)] ZPVE[CCSD(T)]

= =

6 8 1 6 6 1 1 1 6 1 1 1 6 1 1 1

0.639600412 0.048266945 1.766200243 -0.024263909 -1.552658876 -2.034462363 -1.893235840 -1.893235840 0.460317678 0.120858993 0.056746269 1.566090617 0.460317678 0.120858993 0.056746269 1.566090617

0.000000000 0.000000000 0.000000000 0.000000000 0.000000000 0.000000000 -0.892491107 0.892491107 -1.263772364 -2.183945612 -1.280894270 -1.278844290 1.263772364 2.183945612 1.280894270 1.278844290

–270.897366147986 84.2948 kcal/mol

10 0.965144275 2.029789558 0.929792028 -0.414742351 -0.264653999 -1.261450112 0.292366038 0.292366038 -1.163697051 -0.653260588 -2.194572861 -1.231054541 -1.163697051 -0.653260588 -2.194572861 -1.231054541

E[CCSD(T)] ZPVE[CCSD(T)]

= =

0.000000000 0.000000000 0.000000000 0.000000000 0.000000000 0.000000000 -0.892107729 0.892107729 -1.261677277 -2.183655940 -1.268215680 -1.288313033 1.261677277 2.183655940 1.268215680 1.288313033

–271.031992878315 87.9997 kcal/mol

S25  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

TS5 6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 1

0.490647705 -0.686351713 -0.163719514 1.838471588 0.500112898 -1.802076836 0.358502658 0.359438984 -1.198473368 1.722514132 2.320669286 2.509565476 -0.459965463 1.339679083 0.632310392 -2.549504557

-0.190845928 0.429196288 1.361042694 0.351097087 -1.534810320 -0.351970272 2.264378453 0.923160797 1.576233717 1.287298584 -0.399734281 0.512495180 -1.715229165 -1.611144959 -2.328570690 0.127707679

E[CCSD(T)] ZPVE[CCSD(T)]

= =

6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 1

-0.048988690 -0.009982823 -1.179896357 -1.326532410 1.230802775 1.229822860 -2.152378876 -1.105050501 -1.166823991 -2.243481830 -1.329882150 -1.392570577 2.118906129 1.201810444 1.346082059 1.096031839

-0.130212550 -0.613352220 0.859059827 -0.560109353 0.575290606 -0.281336465 0.515697617 1.740635325 1.163168503 -1.132187176 -1.216628519 0.307566316 1.086055779 1.291582216 -0.186257120 -0.660559498

–270.894838749963 86.4413 kcal/mol

12 -0.705800665 0.652392218 1.609225220 -1.520701492 -1.521008653 1.284599997 1.097738668 2.296321623 2.231799433 -0.909170478 -2.190325261 -2.174466618 -0.884328596 -2.276182640 -2.077532575 2.190890142

E[CCSD(T)] ZPVE[CCSD(T)]

= =

0.014426700 0.009223120 0.011633755 -0.020220344 0.019674567 -0.043818760 0.073818771 0.880823426 -0.905157393 -0.060810853 -0.904761399 0.873527845 0.159627608 0.831546996 -0.933345660 0.266549194

–271.011905516161 87.8597 kcal/mol

S26  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

TS6 6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 1

-0.507256272 0.749500726 -0.109616215 -1.787107031 -0.435305613 1.855138349 -0.791405537 0.538368285 0.685960551 -1.765915895 -1.892924605 -2.676223918 0.482156236 -1.313256803 -0.437352285 2.610907063

0.048026540 -0.586349331 -0.921837801 -0.351087885 1.539914420 0.191092615 -1.749820048 -0.544406684 -1.608343436 -1.424077171 0.230736304 -0.163665294 1.789892350 1.845313512 2.131662323 -0.309342203

E[CCSD(T)] ZPVE[CCSD(T)]

= =

6 6 6 1 1 6 1 1 1 6 1 1 1 8 1 1

0.812745821 0.594818279 -0.046279540 1.800540089 0.280872192 0.536398354 0.364063787 0.064762738 1.627750790 -1.551934015 -1.914277859 -2.078854524 -1.821930741 -0.257478446 0.200416781 1.446253598

0.042844227 -0.585394913 1.131146829 -0.693061538 0.366021769 -0.295633390 1.376696863 1.933559358 0.229261349 -0.961369506 -1.628878609 -0.058099344 0.924641419 0.967032909 -0.570402930 -0.634831964

–270.904928570865 85.5292 kcal/mol

11 -0.161735808 -0.751108435 0.572865535 0.245687853 -0.655672752 1.828670914 2.710238347 2.028068843 1.731804764 0.604556902 -0.354473630 0.787758648 1.417746857 -1.859483296 -2.606982388 -0.716785739

E[CCSD(T)] ZPVE[CCSD(T)]

= =

-1.086455022 0.303888491 -0.052687279 -1.339039583 -1.910422967 0.580298719 -0.068701712 1.563035989 0.737200985 -0.272842811 -0.679758324 0.684513791 -0.975100237 0.455205170 0.043931528 1.004303260

–270.993351272383 88.9296 kcal/mol

S27  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

TS7 6 1 8 1 6 1 1 6 6 1 1 1 6 1 1 1

1.718891130 1.771034314 2.396250974 2.390260221 -0.815228027 -1.058249964 -0.329757205 -1.101035527 -0.783333038 -1.713598770 -0.159652379 -0.249795173 -1.776647022 -2.783513055 -1.891851100 -1.173795097

0.816811363 1.482749730 -0.252481954 -0.877339101 0.420858783 1.460182014 -0.192941084 -0.081107701 -1.517177150 -2.076437750 -1.551146969 -2.038895291 0.767174018 1.092511434 0.201284658 1.666272157

E[CCSD(T)] ZPVE[CCSD(T)]

= =

1 6 6 1 6 6 1 1 1 1 1 1

0.938161983 0.000000000 0.000000000 -0.938161983 1.284460718 -1.284460718 2.175710333 -2.175710333 1.332492428 -1.332492428 1.332492428 -1.332492428

-0.411355860 0.501944401 -0.004747106 -0.750496436 1.401975549 1.664539245 2.172788349 0.174881148 -0.191323468 -0.416951423 -1.107214783 0.624149447 -0.897048392 -0.572190310 -1.839642351 -1.119947645

–270.898820271069 84.9750 kcal/mol

14 0.000000000 0.000000000 0.000000000 0.000000000 0.000000000 0.000000000 0.000000000 0.000000000 -0.890499401 -0.890499401 0.890499401 0.890499401

E[CCSD(T)] ZPVE[CCSD(T)]

= =

1 6 8 1

0.938614768 -0.123745909 0.083879600 -0.796423597

2.022752110 1.451411653 0.096771564 2.022752110 -0.709434600 -0.709434600 -0.056554215 -0.056554215 -1.368028918 -1.368028918 -1.368028918 -1.368028918

–156.761485998612 67.4299 kcal/mol

15 -1.137634828 -0.743128479 0.567308550 0.982339948

E[CCSD(T)] ZPVE[CCSD(T)]

= =

0.000000000 0.000000000 0.000000000 0.000000000

–114.135918689421 16.7796 kcal/mol

S28  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

16 8 6 1 1

0.000000000 0.000000000 0.000000000 0.000000000

E[CCSD(T)] ZPVE[CCSD(T)]

0.000000000 0.000000000 0.945634563 -0.945634563 = =

-0.608027718 0.607604879 1.207596971 1.207596971

–114.219033679556 16.6888 kcal/mol

c) Scheme 3: M06-2X/6-311++G(d,p) 9 6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 1

3

0.335066000 -0.901681000 0.819513000 1.373116000 0.121328000 -1.962220000 0.975623000 1.766996000 0.098458000 1.512000000 1.057457000 2.331293000 -0.576999000 1.073434000 -0.277950000 -2.746610000

0.010820000 -0.556192000 -1.144302000 0.253044000 1.276832000 -0.014251000 -2.057008000 -0.855886000 -1.353814000 -0.647461000 1.060607000 0.533910000 1.102791000 1.607325000 2.088073000 -0.405743000

E[M06-2X] ZPVE[M06-2X]

= =

6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 1

-0.002326000 0.025486000 -1.234623000 -0.072271000 1.276901000 0.112207000 -2.155832000 -1.263469000 -1.202694000 -0.977983000 0.790767000 -0.080659000 1.358376000 1.260975000 2.161360000 -0.747500000

0.016511000 0.677701000 -0.885891000 1.119480000 -0.817730000 0.130934000 -0.307922000 -1.348766000 -1.679943000 1.720341000 1.784879000 0.673670000 -1.637914000 -1.240851000 -0.204062000 0.532675000

–271.6395447 0.1414336

9 -0.378233000 0.920136000 -0.411626000 -1.522164000 -0.495903000 2.130051000 -0.330860000 -1.350941000 0.409385000 -1.448570000 -1.497452000 -2.483919000 0.344384000 -1.424016000 -0.500112000 2.568432000

E[M06-2X] ZPVE[M06-2X]

= =

-0.027111000 -0.777259000 0.893476000 -1.040693000 0.819556000 -0.202867000 0.310725000 1.453189000 1.614508000 -1.647447000 -1.709799000 -0.521228000 1.512412000 1.398654000 0.178932000 -0.174831000

–271.5958941 0.1395664

S29  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

TS4 6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 1

-0.045390000 -0.598812000 -0.598812000 -0.598812000 1.482147000 0.232941000 -1.690206000 -0.274653000 -0.232020000 -1.690206000 -0.232020000 -0.274653000 1.874392000 1.854623000 1.874392000 -0.915111000

0.348433000 -1.053560000 1.040064000 1.040064000 0.339846000 -2.044344000 1.013045000 2.083895000 0.558209000 1.013045000 0.558209000 2.083895000 -0.171136000 1.366926000 -0.171136000 -2.269283000

E[M06-2X] ZPVE[M06-2X]

= =

6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 1

0.329519000 -1.085102000 1.026554000 1.026554000 0.312568000 -2.086718000 1.003282000 2.073310000 0.551825000 1.003282000 0.551825000 2.073310000 -0.206266000 1.334911000 -0.206266000 -1.146035000

0.000000000 0.000000000 1.255625000 -1.255625000 0.000000000 0.000000000 1.266335000 1.266539000 2.165047000 -1.266335000 -2.165047000 -1.266539000 0.881555000 0.000000000 -0.881555000 0.000000000

–271.5878486 0.1355462

10 -0.003639000 -0.551004000 -0.551004000 -0.551004000 1.520627000 0.109876000 -1.644206000 -0.237211000 -0.175907000 -1.644206000 -0.175907000 -0.237211000 1.903558000 1.906691000 1.903558000 -1.662036000

E[M06-2X] ZPVE[M06-2X]

= =

0.000000000 0.000000000 1.254386000 -1.254386000 0.000000000 0.000000000 1.278026000 1.260292000 2.164171000 -1.278026000 -2.164171000 -1.260292000 0.880700000 0.000000000 -0.880700000 0.000000000

–271.7211251 0.1413691

S30  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

TS5 6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 1

-0.440456000 0.723604000 0.255866000 -1.779914000 -0.461236000 1.825883000 -0.258592000 -0.237220000 1.283258000 -1.668936000 -2.275857000 -2.421663000 0.467433000 -1.318553000 -0.547887000 2.583769000

0.179235000 -0.408822000 -1.321396000 -0.376390000 1.510600000 0.384075000 -2.220189000 -0.885825000 -1.529082000 -1.300300000 0.360135000 -0.538496000 1.682064000 1.593899000 2.295204000 -0.029372000

E[M06-2X] ZPVE[M06-2X]

= =

6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 1

0.055773000 -0.067884000 1.022555000 1.371194000 -1.155625000 -1.337020000 2.013979000 0.894656000 0.978357000 2.239411000 1.412201000 1.471842000 -2.076919000 -1.079448000 -1.219085000 -1.294917000

-0.155553000 -0.643708000 0.815913000 -0.551916000 0.548651000 -0.341223000 0.498340000 1.696951000 1.097845000 -1.118029000 -1.190797000 0.320048000 1.091039000 1.219487000 -0.208689000 -0.756738000

–271.5979279 0.1391675

12 -0.664115000 0.665505000 1.694345000 -1.392553000 -1.557466000 1.211515000 1.257535000 2.375268000 2.293262000 -0.738358000 -2.065998000 -2.018753000 -0.992832000 -2.292442000 -2.120134000 2.136034000

E[M06-2X] ZPVE[M06-2X]

= =

-0.011257000 -0.003208000 -0.005110000 0.009623000 -0.014593000 0.046239000 -0.081506000 -0.854423000 0.909849000 0.059988000 0.872098000 -0.882936000 -0.139493000 -0.822286000 0.922949000 -0.206882000

–271.7096644 0.141416

S31  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

TS6 6 6 6 6 6 8 1 1 1 1 1 1 1 1 1 1

-0.462204000 0.765381000 0.042011000 -1.762234000 -0.412436000 1.869246000 -0.592177000 0.693735000 0.792012000 -1.721933000 -1.939161000 -2.603778000 0.508883000 -1.262265000 -0.468916000 2.616531000

0.040357000 -0.567258000 -0.911386000 -0.394119000 1.521903000 0.216148000 -1.751238000 -0.510962000 -1.589013000 -1.449725000 0.183608000 -0.239373000 1.791908000 1.796097000 2.105706000 -0.203169000

E[M06-2X] ZPVE[M06-2X]

= =

6 6 6 1 1 6 1 1 1 6 1 1 1 8 1 1

-0.756601000 -0.595039000 0.042274000 -1.724105000 -0.193002000 -0.576675000 -0.389246000 -0.151806000 -1.658179000 1.545355000 1.932912000 2.021242000 1.829339000 0.250492000 -0.171115000 -1.455858000

0.032317000 -0.611779000 1.075153000 -0.620819000 0.356662000 -0.363022000 1.345587000 1.842288000 0.197973000 -0.896540000 -1.531058000 0.061206000 0.870366000 0.985959000 -0.565860000 -0.794945000

–271.6020317 0.1378152

11 -0.249223000 -0.781882000 0.518979000 0.132428000 -0.761004000 1.777761000 2.628034000 2.009977000 1.672909000 0.562809000 -0.385291000 0.765503000 1.357682000 -1.874109000 -2.658855000 -0.739176000

E[M06-2X] ZPVE[M06-2X]

= =

1.090476000 -0.309651000 0.060140000 1.393761000 1.861886000 -0.504994000 0.156954000 -1.485633000 -0.619015000 0.214066000 0.585290000 -0.749345000 0.909159000 -0.526644000 -0.167735000 -0.972388000

–271.695847 0.1427511

S32  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

TS7 6 1 8 1 6 1 1 6 6 1 1 1 6 1 1 1

-1.204286000 -1.338231000 -2.187251000 -2.160942000 0.360375000 0.651565000 -0.279997000 0.778296000 0.519756000 1.438601000 0.216200000 -0.246355000 1.749385000 2.748375000 1.443834000 1.803806000

-0.668951000 -1.645484000 0.085162000 0.940140000 -0.683672000 -1.721379000 -0.255869000 0.042976000 1.523486000 2.072979000 1.798019000 1.841776000 -0.510243000 -0.101806000 -0.233489000 -1.597761000

E[M06-2X] ZPVE[M06-2X]

= =

6 1 8 1 6 1 1 6 6 1 1 1 6 1 1 1

-0.668951000 -1.645484000 0.085162000 0.940140000 -0.683672000 -1.721379000 -0.255869000 0.042976000 1.523486000 2.072979000 1.798019000 1.841776000 -0.510243000 -0.101806000 -0.233489000 -1.597761000

-0.643671000 -0.135864000 -0.161224000 -0.606194000 1.283618000 1.400254000 2.046827000 0.226857000 0.137916000 0.363788000 -0.876312000 0.847129000 -0.779105000 -0.594267000 -1.788924000 -0.720339000

–271.5907693 0.1383598

TS7 -1.204286000 -1.338231000 -2.187251000 -2.160942000 0.360375000 0.651565000 -0.279997000 0.778296000 0.519756000e 1.438601000 0.216200000 -0.246355000 1.749385000 2.748375000 1.443834000 1.803806000

E[M06-2X] ZPVE[M06-2X]

= =

-0.643671000 -0.135864000 -0.161224000 -0.606194000 1.283618000 1.400254000 2.046827000 0.226857000 0.137916000 0.363788000 -0.876312000 0.847129000 -0.779105000 -0.594267000 -1.788924000 -0.720339000

–271.5907693 0.1383598

S33  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

14 6 6 6 6 1 1 1 1 1 1 1 1

0.000000000 0.000000000 0.000000000 0.000000000 0.000000000 0.000000000 -0.879049000 0.879049000 0.000000000 0.879049000 -0.879049000 0.000000000

1.271323000 0.000000000 -1.271323000 0.000000000 0.925800000 -0.925800000 1.313363000 1.313363000 2.153372000 -1.313363000 -1.313363000 -2.153372000

E[M06-2X] ZPVE[M06-2X]

= =

6 8 1 1

0.738124000 -0.564903000 0.974510000 -0.884024000

-0.678377000 0.125374000 -0.678377000 1.456251000 2.020849000 2.020849000 -1.328911000 -1.328911000 -0.037642000 -1.328911000 -1.328911000 -0.037642000

–157.180771 0.1084038

15 0.010906000 0.010906000 -1.075708000 0.923028000

E[M06-2X] ZPVE[M06-2X]

= =

6 8 1 1

0.000000000 0.000000000 0.939422000 -0.939422000

0.000000000 0.000000000 0.000000000 0.000000000

–114.4058595 0.027301

16 0.000000000 0.000000000 0.000000000 0.000000000

E[M06-2X] ZPVE[M06-2X]

= =

-0.525604000 0.671056000 -1.107414000 -1.107414000

–114.487195 0.0270506

S34  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

d) Scheme 5: M06-2X/6-311++G(d,p) neopentanol 6 6 6 6 6 1 1 1 1 1 1 1 1 1 1 1 8 1

-0.348114000 1.179616000 -0.847069000 -0.847069000 -0.847069000 -0.504769000 -0.477663000 -1.940122000 -0.504769000 -1.940122000 -0.477663000 -0.499774000 -1.939819000 -0.499774000 1.530740000 1.530740000 1.669179000 2.627795000

E[M06-2X] ZPVE[M06-2X]

0.208048000 0.235804000 1.655163000 -0.515551000 -0.515551000 -0.005892000 -1.541949000 -0.537754000 -0.005892000 -0.537754000 -1.541949000 2.194098000 1.678997000 2.194098000 0.774706000 0.774706000 -1.096812000 -1.078404000 = =

0.000000000 0.000000000 0.000000000 1.254070000 -1.254070000 2.159856000 1.279363000 1.270684000 -2.159856000 -1.270684000 -1.279363000 0.886465000 0.000000000 -0.886465000 0.890578000 -0.890578000 0.000000000 0.000000000

–272.9299482 0.1656091

neopentylfluoride 6 6 6 6 6 9 1 1 1 1 1 1 1 1 1 1 1

-0.127453000 -0.473200000 0.683848000 -1.444531000 0.683848000 0.683848000 0.941185000 1.609445000 0.112982000 -2.042731000 -2.042731000 -1.244110000 1.609445000 0.941185000 0.112982000 -1.043682000 -1.043682000

E[M06-2X] ZPVE[M06-2X]

0.370435000 -1.112038000 0.704082000 1.151314000 0.704082000 -1.883951000 1.766278000 0.125853000 0.480516000 0.921815000 0.921815000 2.225495000 0.125853000 1.766278000 0.480516000 -1.383059000 -1.383059000 = =

0.000000000 0.000000000 1.255039000 0.000000000 -1.255039000 0.000000000 1.270034000 1.282839000 2.160924000 0.886536000 -0.886536000 0.000000000 -1.282839000 -1.270034000 -2.160924000 0.893501000 -0.893501000

–296.9541951 0.1534134

S35  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

neopentylchloride 6 6 6 6 6 1 1 1 1 1 1 1 1 1 1 1 17

0.654366000 -0.872609000 1.157721000 1.157721000 1.157721000 0.813288000 0.813288000 2.250283000 0.821007000 2.250400000 0.797491000 0.797491000 2.250400000 0.821007000 -1.233633000 -1.233633000 -1.686877000

E[M06-2X] ZPVE[M06-2X]

0.415088000 0.497142000 -0.300490000 1.865395000 -0.300490000 2.405091000 2.405091000 1.881712000 -1.338434000 -0.294748000 0.197081000 0.197081000 -0.294748000 -1.338434000 1.013181000 1.013181000 -1.112113000 = =

0.000000000 0.000000000 1.255637000 0.000000000 -1.255637000 0.886595000 -0.886595000 0.000000000 -1.279468000 -1.277633000 -2.160819000 2.160819000 1.277633000 1.279468000 -0.889573000 0.889573000 0.000000000

–657.3166065 0.1520436

neopentylamine 6 6 6 6 6 7 1 1 1 1 1 1 1 1 1 1 1 1 1

0.422312000 -0.872145000 1.604647000 0.541018000 0.414099000 -2.068878000 2.551379000 1.561005000 1.611869000 0.611994000 -0.333490000 1.437316000 0.264168000 1.366309000 -0.375815000 -2.881432000 -2.262927000 -0.868469000 -0.859343000

E[M06-2X] ZPVE[M06-2X]

0.000805000 -0.604670000 -0.605986000 -0.324940000 1.520213000 -0.034087000 -0.228843000 -0.356721000 -1.696115000 -1.405838000 0.039982000 0.136366000 1.779662000 1.952625000 1.989814000 -0.606352000 0.888352000 -1.679449000 -0.487413000 = =

0.005947000 -0.560777000 -0.753847000 1.496662000 -0.191578000 0.060095000 -0.357832000 -1.818252000 -0.660206000 1.651692000 2.037640000 1.921033000 -1.244930000 0.127370000 0.400178000 -0.134329000 -0.313057000 -0.353068000 -1.655349000

–253.0578269 0.1783369

S36  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

tert.-butylfluorocarbene 6 6 6 6 6 9 1 1 1 1 1 1 1 1 1

-0.329789000 0.827963000 -0.516758000 -1.555911000 -0.091186000 1.937769000 -1.411792000 0.336338000 -0.657379000 -1.690040000 -1.448532000 -2.452376000 0.745489000 -0.986482000 0.118932000

E[M06-2X] ZPVE[M06-2X]

0.027025000 -0.482493000 -1.141795000 0.109292000 1.340453000 -0.031566000 -0.928939000 -1.224600000 -2.095660000 -0.823722000 0.918860000 0.300517000 1.262364000 1.606012000 2.154364000 = =

-0.023543000 -0.829071000 0.983080000 -0.936031000 0.725250000 -0.274694000 1.572469000 1.659150000 0.471479000 -1.486292000 -1.661481000 -0.340763000 1.420026000 1.292391000 0.027157000

–295.  6363097 0.1273517

tert.-butylfluorocarbene_TSins 6 6 6 6 6 9 1 1 1 1 1 1 1 1 1

-0.442274000 0.735051000 0.111782000 -1.777409000 -0.355548000 1.850952000 -0.531290000 0.771551000 0.837830000 -1.757007000 -2.001312000 -2.579542000 0.601354000 -1.155101000 -0.474666000

E[M06-2X] ZPVE[M06-2X]

0.045544000 -0.590333000 -0.918456000 -0.376177000 1.523329000 0.163006000 -1.740231000 -0.504848000 -1.583190000 -1.427246000 0.216589000 -0.229118000 1.782120000 1.798966000 2.116460000 = =

0.031360000 -0.680554000 1.047718000 -0.555308000 0.363722000 -0.426940000 1.349881000 1.801522000 0.247291000 -0.849571000 -1.444903000 0.173313000 0.814710000 1.054884000 -0.546296000

–295.6156339 0.1248099

S37  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

2,2-dimethylfluorocyclopropane 6 6 6 1 1 6 1 1 1 6 1 1 1 9 1

-0.276996000 -0.780002000 0.507155000 0.097445000 -0.813890000 1.777732000 2.615167000 2.023740000 1.680988000 0.523020000 -0.434861000 0.730162000 1.302691000 -1.879682000 -0.789764000

E[M06-2X] ZPVE[M06-2X]

-0.756471000 -0.608124000 0.045150000 -1.722407000 -0.192887000 -0.564548000 -0.375653000 -0.134718000 -1.646226000 1.549772000 1.924913000 2.024451000 1.851194000 0.191993000 -1.451276000 = =

1.085549000 -0.311664000 0.061880000 1.401347000 1.838775000 -0.486130000 0.191231000 -1.460928000 -0.605550000 0.207810000 0.568419000 -0.755012000 0.912101000 -0.493679000 -0.991940000

–295.7165103 0.1303831

tert.-butylchlorocarbene 6 6 6 6 6 17 1 1 1 1 1 1 1 1 1

-0.708641000 0.458056000 -1.009268000 -1.867649000 -0.546184000 1.961745000 -1.943291000 -0.216819000 -1.136090000 -1.978816000 -1.688493000 -2.799043000 0.174441000 -1.508800000 -0.210649000

E[M06-2X] ZPVE[M06-2X]

0.025635000 -0.609625000 -1.058698000 0.045306000 1.393248000 -0.014163000 -0.771502000 -1.101558000 -2.046989000 -0.928787000 0.789965000 0.301368000 1.365235000 1.718156000 2.139684000 = =

-0.031621000 -0.715177000 1.047387000 -1.040740000 0.635203000 -0.108287000 1.536788000 1.796460000 0.603601000 -1.518791000 -1.819396000 -0.529095000 1.452749000 1.037002000 -0.088752000

–655.988041 0.1260547

S38  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

tert.-butylchlorocarbene_TSins 6 6 6 6 6 17 1 1 1 1 1 1 1 1 1

-0.814113000 0.339667000 -0.466348000 -2.116393000 -0.688325000 1.920921000 -1.236883000 0.107423000 0.269581000 -2.151475000 -2.197628000 -2.972200000 0.174940000 -1.588667000 -0.587676000

E[M06-2X] ZPVE[M06-2X]

0.058368000 -0.694628000 -0.978955000 -0.235923000 1.515359000 0.076711000 -1.719787000 -0.621519000 -1.694730000 -1.276035000 0.399189000 -0.037537000 1.692759000 1.826419000 2.141834000 = =

0.013656000 -0.594310000 1.066392000 -0.719165000 0.421872000 -0.208071000 1.265901000 1.913517000 0.396617000 -1.046941000 -1.603922000 -0.067672000 1.060617000 0.956140000 -0.467722000

–655.9727899 0.123591

2,2-dimethylchlorocyclopropane 6 6 6 1 1 6 1 1 1 6 1 1 1 17 1

0.337711000 -0.366023000 0.894457000 0.834729000 -0.134085000 2.116860000 3.026887000 2.166106000 2.105017000 0.825781000 -0.049197000 0.777878000 1.719693000 -1.939064000 -0.335664000

E[M06-2X] ZPVE[M06-2X]

-0.846364000 1.134756000 -0.714476000 -0.180557000 0.060161000 0.060764000 -1.785599000 1.346405000 -0.369224000 1.984878000 -0.408952000 -0.698629000 -0.152303000 -0.149408000 0.067577000 -1.681403000 -1.491467000 -0.843749000 1.554567000 0.276876000 1.839520000 0.860583000 2.076983000 -0.682564000 1.893172000 0.806769000 0.093680000 -0.254331000 -1.540834000 -0.877135000 = =

–656.0794641 0.1291178

S39  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

tert.-butylaminocarbene 6 6 6 6 6 7 1 1 1 1 1 1 1 1 1 1 1

-0.086778000 -0.658805000 -0.658805000 -0.658805000 1.442631000 0.254128000 -0.369076000 -0.283072000 -1.747550000 -1.747550000 -0.283072000 -0.369076000 1.893584000 1.723848000 1.893584000 -0.031219000 1.264069000

E[M06-2X] ZPVE[M06-2X]

0.326621000 -1.084384000 1.012153000 1.012153000 0.461363000 -2.021266000 2.067006000 0.541783000 0.942323000 0.942323000 0.541783000 2.067006000 0.009797000 1.516945000 0.009797000 -2.990971000 -1.866362000 = =

0.000000000 0.000000000 1.250918000 -1.250918000 0.000000000 0.000000000 1.264192000 2.163729000 1.256740000 -1.256740000 -2.163729000 -1.264192000 0.890039000 0.000000000 -0.890039000 0.000000000 0.000000000

–251.7853303 0.1543173

tert.-butylaminocarbene_TSins 6 6 6 6 6 7 1 1 1 1 1 1 1 1 1 1 1

-0.466051000 0.774150000 -0.035320000 -1.748092000 -0.444130000 1.944827000 -0.704396000 0.597402000 0.717766000 -1.703339000 -1.888062000 -2.611754000 0.378496000 -1.369106000 -0.364692000 2.802004000 2.048546000

E[M06-2X] ZPVE[M06-2X]

0.037341000 -0.583408000 -0.902516000 -0.391061000 1.526778000 0.126677000 -1.716711000 -0.510948000 -1.617949000 -1.450556000 0.174426000 -0.221843000 1.814590000 1.818723000 2.101992000 -0.338355000 0.937078000 = =

0.026776000 -0.564435000 1.118388000 -0.668409000 0.329899000 -0.438927000 1.382857000 1.906450000 0.171583000 -0.927016000 -1.593058000 -0.017100000 0.987559000 0.831730000 -0.596855000 -0.683658000 0.156681000

–251.729864 0.1492911

S40  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

2,2-dimethylaminocyclopropane 6 6 6 1 1 6 1 1 1 6 1 1 1 7 1 1 1

-0.199532000 -0.783517000 0.537302000 0.194410000 -0.698304000 1.776191000 2.648563000 1.981484000 1.663678000 0.601350000 -0.331567000 0.783549000 1.421031000 -1.952831000 -0.715720000 -2.787753000 -2.080308000

E[M06-2X] ZPVE[M06-2X]

-0.766551000 -0.597804000 0.043199000 -1.736622000 -0.219721000 -0.573104000 -0.396057000 -0.138715000 -1.652993000 1.542968000 1.928945000 2.036303000 1.808430000 0.236107000 -1.467962000 -0.272341000 0.565729000 = =

1.091814000 -0.287366000 0.058193000 1.369272000 1.882928000 -0.552972000 0.082903000 -1.536058000 -0.675479000 0.234526000 0.643312000 -0.725605000 0.908355000 -0.399197000 -0.939562000 -0.131469000 -1.349393000

–251.826502 0.155532

S41  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

5) Crystal data and structure refinement for the dimer of 13 Cell parameters were refined by using up to 2346 reflections. A sphere of data (190 frames) was collected with the φ-oscillation mode (0.7° frame width; Irradiation times/frame: 12 min). The refinement shows the full molecule in the independent unit of the elementary cell. All C-H hydrogen atoms were positioned geometrically, the O-H hydrogen atoms were found and isotropically refined.

  Figure S23: Ortep plot with thermal ellipsoids set at 50 % probability shows the full molecule.   CCDC-no. Empirical formula Formula weight Temperature Wavelength Crystal system, space group Unit cell dimensions

Volume Z, Calculated density Absorption coefficient F(000) Habitus, color Crystal size

900416 C12H20O6 260.28 193(2) K 0.71073 Å Monoclinic P21/c a = 6.069(6) Å α = 90.000(0) b = 11.699(13) Å β = 98.695(11) c = 19.438(19) Å γ = 90.000(0) 1364.3(2) Å3 8 1.267 Mg/m3 –1 0.101 mm 560 Block colourless 0.25 mm x 0.24 mm x 0.18 mm S42

 

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

Theta range for data collection Limiting indices Reflections collected / unique Completeness to theta = 26.99 ° Absorption correction Refinement method Data / restraints / parameter Goodness-of-fir on F2 Final R indices [I > 2 σ(I)] R indices (all data) Largest diff. peak and hole

3.63 ° to 26.99 ° –7 ≤ h ≤ 7, –14 ≤ k ≤ 14, –24 ≤ l ≤ 24 11071 / 2774 [R(int) = 0.0487] 93.2 % None Full-matrix least-squared on F2 2774 / 0 / 165 0.686 R1 = 0.0414 wR2 = 0.1566 R1 = 0.0480 wR2 = 0.1452 –3 0.35 and -0.17 e Å

Bond lengths [Å] and angles [°] O(1)-C(7) O(1)-C(13) O(2)-C(10) O(2)-C(7) O(3)-C(9) O(4)-C(13) O(5)-C(9) O(6)-C(10) C(7)-C(8) C(7)-C(9) C(8)-C(15) C(8)-C(16) C(8)-C(12) C(10)-C(13) C(11)-C(14) C(11)-C(17) C(11)-C(18) C(11)-C(13) C(7)-O(1)-C(13) C(10)-O(2)-C(7) O(1)-C(7)-O(2) O(1)-C(7)-C(8) O(2)-C(7)-C(8) O(1)-C(7)-C(9) O(2)-C(7)-C(9)

1.4007(15) 1.4240(13) 1.3374(17) 1.4396(13) 1.2325(16) 1.4003(13) 1.2705(16) 1.2012(15) 1.5428(17) 1.5459(15) 1.526(2) 1.5294(19) 1.5323(17) 1.5437(18) 1.5258(18) 1.527(2) 1.527(2) 1.5322(18) 106.97(9) 108.68(10) 105.59(9) 110.62(9) 109.37(10) 110.07(10) 107.70(9)

O(6)-C(10)-C(13) C(14)-C(11)-C(17) C(17)-C(11)-C(18) C(17)-C(11)-C(13) O(4)-C(13)-O(1) O(1)-C(13)-C(11) O(1)-C(13)-C(10) C(8)-C(7)-C(9) C(15)-C(8)-C(16) C(15)-C(8)-C(12) C(16)-C(8)-C(12) C(15)-C(8)-C(7) C(16)-C(8)-C(7) C(12)-C(8)-C(7) O(3)-C(9)-O(5) O(3)-C(9)-C(7) O(5)-C(9)-C(7) O(6)-C(10)-O(2) O(2)-C(10)-C(13) C(14)-C(11)-C(18) C(14)-C(11)-C(13) C(18)-C(11)-C(13) O(4)-C(13)-C(11) O(4)-C(13)-C(10) C(11)-C(13)-C(10)

130.11(13) 108.73(12) 110.21(15) 108.89(10) 110.71(9) 109.28(9) 100.75(10) 113.18(10) 109.69(13) 110.26(11) 109.24(12) 109.79(11) 108.53(10) 109.30(11) 125.93(11) 118.27(11) 115.79(10) 122.20(13) 107.69(9) 109.79(12) 110.10(12) 109.10(12) 114.69(11) 104.14(9) 116.34(10)

S43  

Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2012

e) Full references for electronic structure codes a) Gaussian09, Revision B.01 M. J. G. W. Frisch, H. B. Trucks, G. E. Schlegel, M. A. Scuseria, J. R. Robb, G. Cheeseman, V. Scalmani, B. Barone, G. A. Mennucci, H. Petersson, M. Nakatsuji, X. Caricato, H. P. Li, A. F. Hratchian, J. Izmaylov, G. Bloino, J. L. Zheng, M. Sonnenberg, M. Hada, K. Ehara, R. Toyota, J. Fukuda, M. Hasegawa, T. Ishida, Y. Nakajima, O. Honda, H. Kitao, T. Nakai, J. A. Vreven, Montgomery Jr., J. E. F. Peralta, M. Ogliaro, J. J. Bearpark, E. Heyd, K. N. Brothers, V. N. Kudin, R. Staroverov, J. Kobayashi, K. Normand, A. Raghavachari, J. C. Rendell, S. S. Burant, J. Iyengar, M. Tomasi, N. Cossi, J. M. Rega, M. Millam, J. E. Klene, J. B. Knox, V. Cross, C. Bakken, J. Adamo, R. Jaramillo, R. E. Gomperts, O. Stratmann, A. J. Yazyev, R. Austin, C. Cammi, J. W. Pomelli, R. L. Ochterski, K. Martin, V. G. Morokuma, G. A. Zakrzewski, P. Voth, J. J. Salvador, S. Dannenberg, A. D. Dapprich, Ö. Daniels, J. B. Farkas, J. V. Foresman, J. Ortiz, J. Cioslowski, D. J. Fox, Gaussian 09, Revision A.1, Gaussian, Inc., Wallingford, CT, 2010.

b) CFOUR, Version 1.0 CFOUR, a quantum chemical program package written by J.F. Stanton, J. Gauss, M.E. Harding, P.G. Szalay with contributions from A.A. Auer, R.J. Bartlett, U. Benedikt, C. Berger, D.E. Bernholdt, Y.J. Bomble, L. Cheng, O. Christiansen, M. Heckert, O. Heun, C. Huber, T.-C. Jagau, D. Jonsson, J. Jusélius, K. Klein, W.J. Lauderdale, D.A. Matthews, T. Metzroth, D.P. O'Neill, D.R. Price, E. Prochnow, K. Ruud, F. Schiffmann, W. Schwalbach, S. Stopkowicz, A. Tajti, J. Vázquez, F. Wang, J.D. Watts and the integral packages MOLECULE (J. Almlöf and P.R. Taylor), PROPS (P.R. Taylor), ABACUS (T. Helgaker, H.J. Aa. Jensen, P. Jørgensen, and J. Olsen), and ECP routines by A. V. Mitin and C. van Wüllen. For the current version, see http://www.cfour.de.

c) ORCA, Version 2.8 F. Neese, U. Becker, D. Ganyushin, S. Kossmann, A. Hansen, D. Liakos, T. Petrenko, C. Riplinger, F. Wennmohs, ORCA, Version 2.8, University of Bonn, Germany, 2009 F. Neese, WIREs Comput. Mol. Sci., 2012, 2, 73–78.

S44