[Fe2(CO)6(/J-SN)]_ (2) which reacts with halides of phosphorus, arsenic, silicon, germanium, tin and boron by formation of ..... Fe2(CO)6[/i-SN-P(NCBu)CH2)->CH'>] (7b) (1 g in C7DS,. -20°C. ..... (C6D6): 6i3C = 20.2 (C(CH3)3), 27.9 (C(CH3)3), 128.1 (o-. Ph), 131.0 .... C2H6, 80), 402 (M+-12CO-OMe2, 15), - IR (cm-1):.
N-Functionalization of the Tetrahedrane Fe2(CO)6(/z-SNH) Max Herberhold*, U w e Bertholdt, Wolfgang M iliu s, Bernd W rackmeyer Laboratorium für Anorganische Chemie, Universität Bayreuth, D-95440 Bayreuth Dedicated to Prof. Dr. Lothar Beyer on the occasion of his 60th birthday Z. Naturforsch. 51 b, 1283-1289 (1996); received March 27, 1996 Azadiferrathia, Tetrahedrane, Cluster Anion, Element-Nitrogen Bonds, NMR Spectra The azadiferrathia tetrahedrane, Fe 2(CO) 6(£/-SNH) (1), was deprotonated to give the anion [Fe 2(CO) 6(/J-SN)]_ (2) which reacts with halides of phosphorus, arsenic, silicon, germanium, tin and boron by formation of element-nitrosen bonds. The new compounds were characterized by their IR. N M R ('H , mB, i3C, i5N, 29S i,3 P, m S n)and mass spectra. The molecular structure of [Fe2(CO)6(A/-SN-SiMe2CH 2-)]2 (11) was determined by X-ray structure analysis (space group P i; triclinic; a = 799.8(2), b = 958.5(2), c = 1035.7(2) pm, a = 86.30(2)°, (3 = 81.27(2)°, 7 = 69.90(2)°).
Introduction
Results and Discussion
The reaction of carbonyliron complexes with bis(trimethylsilyl)sulfurdiimide, M e3Si(NSN)SiMe3, followed by chromatography on silica, leads to the azadiferrathia tetrahedrane 1 [1]. The corresponding anion 2 is formed by deprotonation using sodium [2], "BuLi in hex ane or DBU (l,8-diazabicyclo[5.4.0]undec-7-ene) [3] [eq. (1)]. It was already shown that 2 reacts with Me^'BuSiCl to give the N-silylated complex Fe2(CO)6(//-SN-SiM e2'Bu) [2], and that N-organosubstituted derivatives Fe2(CO)6(/u-SN-R) are ac cessible from the reaction of 2 with carbenium or trialkyl oxonium cations [3], These successful trans formations of 2 prompted us to start a systematic study of the N-functionalization of 1. Here we de scribe the new complexes which contain group 15 (phosphanyl, arsanyl), group 14 (silyl, germyl. stannyl) and group 13 (boryl) substituents at the nitrogen atom.
Syntheses
(i)
/ N ------S
/> < S \
x
-N»7
V
A
-------- 5Ü---------C4H10, -Li
(OC)3Fe —---------Fe(CO )3 \
DBU
f
©
N S
/X \\
(OC^Fe -- ---------Fe(CO>3 2
* Reprint requests to Prof. Dr. M. Herberhold. 0 9 3 9 -5 0 7 5 /9 6 /0 9 0 0 - 1 2 8 3 $ 0 6 .0 0
The reactions of the anion 2 with various element halides are summarized in Scheme 1. Apparently, any triorganosilyl, -germyl or -stannyl chloride can be used to prepare complexes of the type 3 - 5 . The reactions of 2 with bis(chlorosilyl) compounds, as shown in Scheme 2, afford the new compounds 9 - 11, of which 11 was studied by X-ray diffraction (vide infra). It appears that the reaction of 2 with arsenic chlo rides is also straightforward, and the products 6a and 6b are isolated in moderate to good yields. In con trast, 'BU2PCI does not react with 2. If the reaction of 2 with either 'P nP C l or Cy2PCl is monitored by IR spectroscopy , the presence of the desired prod ucts can be observed for about 5 - 1 0 min at -78°C, but thereafter decomposition into unidentified com pounds takes place, as is also apparent from the 11P NMR spectra of reaction solutions. However, it turns out that 2 reacts with cyclic diaminophosphorus halides bearing bulky substituents ('Bu groups) at the nitrogen atoms to give reasonably stable prod ucts (7a, 7b). Compounds 7c and 7d with the less bulky N 'Pr groups had to be characterized at low temperature. The boron-substituted tetrahedranes 8 can be readily isolated if at least one dialkylamino group is linked to boron. All attempts to obtain dialkylboryl derivatives failed. Although 2 reacts with the 9-BBN derivatives 9-chloro- and 9-methoxyborabicyclo[3.3.1jnonane, it was not possible so
© 1996 Verlag der Z eitschrift für N aturforschung. A ll rights reserved.
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et al. ■N -F un ctionalization o f the Tetrahedrane Fe 2 (C O ) 6 (//-S N H )
M. H erberhold
R,R'M
\ N ------S
/ ,X
\
(OC )3Fe ______ _ Fe( CO)3 3. 4. 5
A tßu,A s
\
R
R'
Si
Me
Me
3b
Si
Me
H
3c
Si
Me
‘Bu
3d
Si
Me
S iM e,
3e
Si
'Bu
H
3f
Si
Ph
’Bu
4
Ge
Me
Me
5a
Sn
Me
Me
5b
Sn
Et
Et
R,RM C1
N ------S
/X
M 3a
}
-er
,
-er \
6a
©
(
R
R
/ > v f
( p
PCI
N ------S
N ------S
-CI
(O C ),F c _ ------- _F e (C O )3
r °, As kÖ \
R
R
(OC)3F e _ ______ F e(C O )3 ^ \ t B u , A s C l
/X
\'
(OC)3Fe _____ _ Fe(CO)3
ASCI. f
R
N ------S
A X s>
(OC)3Fc ______ _ F e (C O )3
‘Bu
(C H ,),
R RBC I
7b
‘Bu
(C H ,),
-er
7c
'Pr
(C H ,),
7d
‘Pr
(S iM e ,),
6b
RR'B 8a
N ------S
/X c
(OC)3Fe ______ _ F e (C O )3
S c h e in e 1
\
7a
R
R
N'Pr,
N'Pr,
8b
N (B u )C H :C H :N B u
8c
N M e2
Fe
^ SiMe,SiMe2v^
sr > N
'
'
n —-
s
//W /x \\ (OC)3Ft------------Fe(CO)3 (OC)3Fe-------------Fe(CO )3 9
CISiMe2SiMe2Cl
-2CI"
° Nc > s
2 /^ \N (OC)3F e—--------- Fe(CO)3 ClSiMe2CH2CH2SiMe2Cl
ClSiMe2OSiMe2Cl
-2 CI'
-2 C r
^ SiMe2CH 2CH 2SiMe^
^ SiMe,OSiMe,^ S - —- N
// X
S ----- N
N ----- S
\
/ X
o
/ / V
(OC)3Fe------------Fe( CO )3 (OC )3Fe - ---------- Fe(CO)3
----- S
\
/X
(OC)3Fe------------Fe(CO )3
11
10 Scheine 2
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\-
(OC) 3Fe------------Fe(CO)3
M. H erberhold
et al. • N -F unctionalization o f the Tetrahedrane F e 2 (C O ) 6 (//,-SN H )
Table I. I5N, 2ySi and 31P NMR data of the tetrahedranes 3 and 7 (chemical shifts [ppm], coupling constants [Hz], solvent: CaD^, 25°C).
b'5N 3a 3b 3c 3d
-359.2 -370|al -371.0 -362.1
3e 3f
-374,0
), 32.1 (SiM ei) 30.8 9.8
[d] ] (7b) (1 g in C7DS, -20°C.
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et al. ■N -F un ctionalization o f the Tetrahedrane Fe 2 (C O ) 6 (^ -S N H )
Table II. Selected bond lengths |pm] and angles [°J in [Fe2(CO)6(//-SN-SiM e 2CH 2‘'-)]2 (11). S -N Fe( 1) - Fe(2) Fe( 1) - N F e(2 )- N F e(1)- S F e(2 )- S N -S i F e ( l) - C ( l) F e(1 ) - C(2) F e(1 ) - C(3) F e (2 )- C(4) F e(2 )- C(5) F e (2 )- C(6) Si - C(7) C(7) - C(7A) C (l) -0 ( 1 ) C(2) - 0 (2 ) C (3 )- 0 (3 ) C(4) - 0 (4 ) C(5) - 0 (5 ) C (6 )- 0 (6 ) Si -C (8) Si - C(9)
169.2(3) 250.6(1) 194.8(3) 194.4(2) 219.8(1) 220.7(1) 178.5(3) 179.5(4) 179.3(3) 180.8(3) 180.2(4) 180.2(4) 179.7(3) 186.5(3) 154.3(6) 113.6(5) 113.7(4) 113.2(4) 112.6(5) 113.1(5) 113.7(4) 185.2(3) 185.5(3)
Fe( 1)- S - Fe(2) Fe( 1) - S - N Fe(2) - S - N Fe( 1) - Fe(2) - S Fe(2) - Fe( 1 )- S N - Fe( 1) - S F e(l) - N -Si Fe(2) - N -Si S - N - Si C(8) - Si - C(9) Si - C(7) - C(7A) Fe( 1) - N - Fe(2) Fe( 1) - N -S Fe(2) - N -S Fe( 1) - Fe(2) - N F e (2 )- F e(l) - N N - Fe(2) - S N - Si - C(7) N - Si - C(8) N - Si - C(9) C(7) - Si - C(8) C(7) - Si - C(9)
69.4( 1) 58.4( 1) 58.0(1) 55.1(1) 55.5( 1) 47.7(1) 134.3(1) 138.9(2) 129.1(1) 112.7(1) 116.3(4) 80.2(1) 73.9(1) 74.4( 1) 50.0(1) 49.8(1) 47.6(1) 108.8(1) 103.4(1) 107.4(2) 112.6(2) 111.5(1)
hood to an ammonium-type nitrogen atom causes deshielding for 29Si [6, 7], and also for 11B [ 11 J ,31P [12], and ll9Sn [13]. A comparison of the relevant data for compounds 3, 5, 7 and 8 shows the same trend. Therefore, the bonding situation at the nitro gen atom corresponds to that of an ammonium-type nitrogen, at least as far as the element-nitrogen bond is concerned. The