Solvated transition metal cations containing weakly bonded organic ligands are potâ¬ntially useful as intermediates in Preparative coordination chemistry.
48. TeIrakisQ)ropaneniI le]lplaIinum(II) tfifuorome thanesuAonate
methane, and insoluble in ethanol, diethyl ether, and toluene. The melting
poinl is 2'14-276"C(capillary).IR spectrum(KBr pellet, cm-r.1: 33Em-s v(Ptcl,) and 315m v(PtCl,).1e5PtNMR spectrumin (CH3)rNCHO,6: - 1381ppm relarive to 0.7 M { (z-CrHs)+N}z[PtClo] in CH2CI2.Crystal data parametersobtainedby X-ray single-crystalmethod:monoclinic,space grotp P 2tlc, a:9.s32(7), b : 15.676(7), c:22.s9(l) A, B : 101.1(5f, v : 3311(3\ 4". References L V. Yu. Kukushkinand Yu. N. Kukushkin,sox.J. Coord.Chem.(Engl.Tronsl.),14,893(f988I Koord.Khim.,14,1587(1988). 2. J. K. Rufl and W. J. Schlientz,/norg. Srnth.,15,84 (1974). 3. V. Yu. Kukushkin and A. l. Moiseev,Inorg. Chim.Acta, t76, 79 (1990). 4. F- J. Lafor and S. Chaon , J. OryanometCrterr.,3,14,163(1988). 5. V. Yu. Kukushkin,v. M. Tkachuk,L A. Krol, Z. A. Starikova,B. v. Zhadanov,and N- P. Kiseleva,J. Gen.Chem.(Engl. Transl.),61,42 (1991\,Zh. Obsch.Khin. 61, 5l (1991'1. J. Coord.Chem. 6. V. Yu. Kukushkin,E. Yu. Pankova,T. N. Fomina,and N. P. Kiselera,So1). lEnsL 7'runsl.l,14,625(1988);Koord. Kldn., 14, lr10 (1988).
48. TETRAKIS(PROPANENITRILE)PLATINUM(II) TRIFLUOROMETHANESULFONATE AS A SUITABLE INTERMEDIATE IN SYNTHETIC Pt(D CHEMISTRY SUBMITTEDBY VADIM YU. KUXUSHXIN,*t,i1g 9561P5595,I r LARSI. ELDINGT RI CHECXEDBY S.JONASDOI-TI Solvatedtransitionmetal cationscontainingweakly bondedorganicligands are pot€ntiallyusefulasintermediatesin Preparativecoordinationchemistry. The coordinatedsolventmoleculesprovide solubility of the compoundsin variousorganic solvents,and th€y can be replacedreadily by other ligands with betterdonor properties.l'2 The preparationof mononucl€artransition metal complexeswith weakly bondedanionshasbeendescribedpreviously3 and preparativeapplicationsof suchcomplexeshave beenreviewed.4 + On l€avefroft Departmentofchemistry, St.PctersburgStateUniversity,UniversitetskyPr. 2, 198904StaryPetergolRussianFedention. V. Yu. K. is grat€fulto the RoyalSwedishAcademy of Russiafor financialsupport of his stay al Ltrnd and the Academyof Sciences of Sciences Univenity. t Inoiganic Chemistry 1, CbemicalC€dter,Lund University, P.O. Box 124,5-22100 Lund, Sweden. t Departmentof Chefiistry, The Universityof Michigan,Ann Arbor, MI 48109.
Herein we describethe preparation of [pt(CrH5CN)a](SO3CF3)2and proposeits use as an intermediatefor the synthesisof other platinum(Il) complexes. The two-stepsFthesis includesthe lormation oI [ptclr(CrH5clgr]5 followed by abstractionof lhe two chloride ligands of this compound by the useof 2 equiv of AgSO3CF3,yieldingthe [ft(CrHsCI.04]r+ solvatedcation.6 A similar procedurehas beendescribedearlier for preparationof the very + moisture-sensitive [P(CH3CN)4], complex.Ts The usefulpropertiesof the IPt(C2H5CN)4](SOrCF3),compoundinclude excellentsolubility in commonlyusedorganicsolvents,relativcinsensitivity to atmosphericmoisture,a fairly high thermal stability, and good leaving propertiesof the coordinatedpropanenitrile.As an exampleof synthesisof oth€r Pt(II) compoundsvia substitutionofthe weaklyboundpropanenitriles, we also describethe reactionof [Pt(CrH5CN)a](SO3CF3),with thioeth€rs resultingin the formation of [Pt(thioether)n](SO3CF3)2 compounds.This methodis more convenientthan the previouslyusedproc€durestartingftom +.e tetraaquaplatinum(ID, [Pt(HrO)4], r Caution. Silaertrifuoromethanesulfonate is an irritant. propanenitrile, thioethers,and all organicsohtentsusedare bxic. Contad wirh the liquids and uaporsshouklbe auoided.Apprcpriateprccautionsmustbe taken,and an eficient hoodmustbe used. A. DICHLOROBIS(PROPANENITRILE)PLATINUM (II) Kr[PtCl4] + 2CrH5CN --+[ptCl3{CrH5CN)r]+ 2KCl Procedure Propanenitrile,C2H5CN(10mL, 140mmol),is addedto a solutionof 10.00s (24mmol) Kr[PtCl4] in 80 mL of water in a 200-mL beaker.The beakerii coveredwith "Parafilm M" and left to stand for 3 days at 20_25.C.The resulting lemon-yellowrodJike crystals are filtered off, washedtwic€ on a filter with 5-mL portions of water, and dried in air at 70"C.The yield of [Ptclr(CrH5CN)r] is 7.36g (81%,basedon pt). Anal. Calcd.Ior lPtCl(crH5CN)rl: Cl, t8.9yo;pt 51.9%.Found:cl, 18.9%;pt, 51.7 %. I Properties The cornpoundobtainedas describedaboveis in fact a 6: 1 mixture of cis_ and trans-isomers asdeterminedby TLC or by NMR spectroscopy. The TLC is carriedout on SiO, Merck Kieselgel.60 F254plates:R7(cis):0.55(larger.
48. Tettukir(lropanenitrile)plotinu
lll) hifuoromethanesuYonate
281
s p o t ) ,R l t r a n s ) : 0 . 8 2 I C H C I 3 : ( C H 3 ) 2 C O1: : 1 , i n v o l u m e ] .l H N M R spectrumof cis-[PtCllCrH5CN)r] in CDrCl, (99.5I atorn 9/oD) d, ppm: l . 4 l [ t , J H H : 7 . 6 H z C H z ] , 2 8 6 [ q , J n n: ' 7 . 6H z , C H z ] . 1 HN M R s p e c t r u r n of tr4ns-[PtCl2(C2H5CN)r] in CD2CI2(99.6+ atom % D) d, ppm: 1.38 [t, JRH: 7.6Hz CH3f, 2.88 [q, JHB: 7.6H2, CHz]. The compound [PtClr(CrH5CN)r] is readily soluble in dichloromethane,acetone,nitromethane,and propanenitrile,sparinglysolublein chloroform,and insoluble in ethanol,diethyl ether,and toluene.The solubility in water at 2O-25"Cis - 5 . l0 3 M. The aqueoussolution becomesblue-coloredin a few days. Electronic absorption spectrumin chloroform: ,l-., 319nm (lge: 2.3).10 Refractiveindices:n, : 1.504,n, : 1.737.rrIR spectrumin KBr pellet,cm - r: 2314m-wv(CN) !it.2303 v(CN)1.l' .13The meltingpoint in a capillary is 112-114"C(it. 116'C5)with subsequent crystallizationol the rrcnslPtclr(CrH5CN)r] from the melt. The newly formed solid melts at 179 182"C.DTA analysis:heating rate is 2.5deg/min; 105'C, endopeak; 110"C,exopeak(lit.: 112'C,endopeak;130"C,exopeakll).
B. TETRAKIS(PROPANENITRILE)PLATINUM(ID TRIFLUOROMETHANESULFONATE [PtClr(CrH5CN)r]+ 2AgSO3CF]] 2C2H5CN'.+ [Pt(CrH5CN)4](SO3CF3 ), + 2AgCl
Procedure The reaction is carried out in a 100-mL Erlenmeyer flask. Silver trifluoromethanesulfonate (2.77g, 10.8mmol), AgSO.CF., is addedto a solution of 1.93g (5.1mmol)oi [PtClr(CrH5CN)r]in 35mL of dichloromethane and 0.9mL (12.8mmol) of propanenitrile.The suspension is stirredvigorouslyon a magnetic stirrer for 5 h. The light yellow solution is filtered from the precipitatedsilver chloride on a Millipore filter (type HY, 0.45pm) into a 100-mL,round-bottomedflask.The precipitateon the filter is washedtwic€ with 2-mL portionsof CH2CI2.The solventis removedundervacuumby use ofa rotary evaporatorat 20 25'C. Thejelly-likeresidueis dissolvedin 15mL of propanenitrileand filtered through paper filter (Munktell Filter Paper Vl20H wasused)into a 400-mLbeaker.Diethyl ether(250mL) is addedand resultsin the immediateformation of a white precipitate.The precipitateis collectedon a filter, washedthreetimeswith 5-mL portionsof diethyl ether, and dried in a ffow of dry argon at 2O-25"C.Yield of [Pr(CrH5CN)a](SO3CF3),, is 2.20g (60%, basedon Pt).
Anal.,Calcd. for [Pt(CrH5CN)n] (SO3CF3)r: C, 23.6yo; H, 2.8yo; N, t.9o/r;
Pt, 273%. Found: C, 23.3%;H, 2.80/":N, j .5V":pt, 2j.2o/".
Properties The [PI(CrH5CN)4] (SO3CF3), is readily soluble in dichloromethane, chloroform,propanenitrile,nitromethane,ethanol,and water. In the latter case a light blue coloration of the solution is observedwithin I h after dissolution.The compoundis sparing.lysolublein diethyl etherand toluene and insoluble in hexane.The melting point in a capillary is 175.C. IR spectrum in Nujol, cm-r: 2334 (CN). rH NMR spectrum in CD2CI2 (99.6+ atom,yoD) d, ppm: l.4t [t, JHH: 7.5 Hz, CH3], 3.30 [q, Jn, : 7.5Hz, CHl. C. TETRAKIS(DIMETHYI.SULFIDE)PLATINUM(II) TRIFLUOROMETHANESULFONATE [Pt(CrHscN)4](so3cF3)2* 4(CH3)rS__+ lPr {(cH3)rs}41(so3cF3)2+ 4C2HsCN Procedure Dimethylsulfide(0.32mL,4.zl0mmol) is addedto a 30-mL beakercontarnrns a. solution of 0.52g (0.73mmol) of [ft(CrH5CN)4](SO3CF3), in 5 mL o] dichloromethane. A colorlessprecipitateof the desired"o*pound is formed immediately.Diethyl ether (5 mL) is addedto the reaction;ixture and the solid is filteredoff, washedon a filter twicewith 2 mL of (C2Hr)rO,and dried in air.at20-25"C.Yield of [Pt{(CH3)rS}4](SO3CF3), i, O.+lg-11.1,h, uasea on Pt). Anal. Calcd' for [Pt {(CH3)rS}4](SO3CF3)2: C, 16.2yo;H, 3.3%; pt,26.3%. Found: C, 16.5%;H, 3.2%:pt,26.3%. D. TETRAKIS(I,+OXATHIANE)PLATINUM(ID TRIFLUOROMETHANESULFONATE AND BIS(I,+DITHIANE)PLATINUM(II) TRIFLUOROMETHANESULFONATE | IPt(CrH5CN)41(SO3CF3)2 + 4S(C2Ha)2O-* lpr {S(CrH4)rO}41(SO3CF3 ), + 4C2HsCN __r lPt(CrH5CN)41(SO3CF3)2 + 2S(C2Ha)2S [Pt{S(CrH4)rS}r](SO3CF3), + 4CrH5CN
48.Tetrakis,)ropanenitrile)platinun(Il)t 283 fuorcmethanesuyonate Procedure The samemethod as that describedfor the preparationof [Pt{(CH3)rS}n](SO]CF3), is used for the synthesisof tetrakis(1,4-oxathiane)platinum(Il) trifluoromethanesulfonate, [ft {S(CrH4)rO}4](SO3CF3)r,and bis(1,4dithiane} platinum(II)trifluoromethanesulfonate, The [Pr{S(CrHa)rS}r](SO3CF.).. yieldsare 867o. Anal. Calcd.for [Pt {S(CrHn)rO}a](SO3CF.)r: C, 23.8Vo;H, 3.6To;Pt, 21.470;Found: C,23.7oh;H, 3.6oh;Pt,21.4o/o. Anal. Calcd..for [Pt{S(CrHa)rS}r](SO3CF3)r: C, l6.4yot H,2.2o/o; Pt, 26.6Yo. Fowd: C, 16.8'/0; H,2.2%; Pt,26.50/..
Properties The [Pt t(CH3)rS]al(SO3CF3)2 compoundis readilysolublein nitromethane and dimethylformamide,sparingly soluble in acetone,ethanol, and water, and insolublein diethyl ether, tolu€ne,and hexane.lH NMR sp€ctrumin CD3NO2(99yo+ atomo D) d, ppm: 2.76(Ip'ff:45.3H2\.ra The melting point in a capillary is 241-243'C(lit. 229-2T'C\. The compoundcrystallized from water belongs"to a space group P 21lc wlth^ a: 8.563q8), b:8.692(1), c= 16.360(3)A, v: 1208.412\ A', and Z=2. A = 96.06a{9\", The Pt-S bond lengths are:2.317(3),2.315(3\,2.319(4),and 2.321(4) i\.e Th€ [Pt {S(CrHa)rO}4](SO3CF3),compoundis readily solublein nitromethaneand dimethylformamide,slightly soluble in acetone,ethanol,and waterand insolublein diethylether,toluene,and hexane.rH NMR spectrum in CD3NO, (99o + atomyo D) d, ppm: 3.04 (d), 4.05(t),Ins:12.3Hz, 3.51(t),4.30(d),Jnx: ll Hz. The melting point in a capillary is 23V232"C (llt. nA-232'Ce). The compoundcrystallizesfrom undried nitromethaneas a monohydrale in space group C 2lc with- a : 14.438(2),b: 13.016(2), c : 2r.696Q)A, P : 126.32(l)",r: 3285.0(6) Ar, andZ : 4. Tbe pr-S bond lengthsare:2.321(21 and,2.3 t 8(2)4.' (SO3CF3),compoundis readilysolublein nitroThe [Pt {S(CrHa)rS}r] methaneand dimethylformamide,slightly solublein acetone,ethanol,and water, and insolublein diethyl ether, toluene,and hexane.lH NMR spectrum in CD3NO, (99Yo+ atomyo D) 6, ppm: 3.19 (Jp,H= 70.0Hz), 3.61 (Jns: 8.8Hz).ra The compound has no characteristicmelting point. On heatingin a capillary it decomposes> 250'C. The [Pr {S(CrH4)rS}r](SO3CF3)2 crystallizesfrom ethanolin spacegroup Pznb wilh a : 11.30q2), b : 12.7s9(r\,c : 14.'tr2Q\A, v : 2122.6G) #, ind Z : 4. The pt-S bond lengthsare: 2.299(2)and 2.302Q)A.t5
References 1. J. A. Daviesand F. R. Harttey,Chem.Reu..tt, j9 lt98t]|. 2. K. R. Dunbar.Comm?nts tnorg.Cren..lJ, ltJ rt992j. L W. L. Drjessendnd J. Reedijk,tnory. Syhth..29, | | | tlsglt. 4. V- Yu. Kukushkinand yu. N. Kukushkin,Theoryand pradice of Coordination Compouwls S/nrlesis,Nauka, Leningrad:1990,p. 45. 5. V V. Lebedinskiiand V. A. Golovnya,,4aa.sectewplatine, Inst. chim.gan.,lt, JE (1945); Chem.Abst..41.6tE7d. 6. V. Yu Kukushkin,A. Oskarsson,and L. L Elding,Zh. Obshch.Khin.,64, 881(t994). 7. A. de Renzi,A. panunzi,A. Viragliano.and c. piiaro, Chem.C"^..,4j it:i;. 8. F. x.. Hartley,S. G. Murray, and C. A. McAuliffe,1nor9.Chen., tt, i3g4'Og;g\. 9. Z. Bugarcic,B. Nor6n,A. oskarsson,C. Stethnaste, anj L. L eiji ng,, orro Ei" l s*^a., $, 3 6 1{ 1 9 9 1 ) . 10. V. A,.colovnya and Ni Chia-Chiang,Russ.J. lnory. Chem.lEngl. frarrt), 6, 6l (1961); Zh. Neorg.Khin.6, 124,196l). ll. V A..Golovnyaand Ni Tszya-Tszyan,Russ.J. Inorg. Chen. \Engl. Iransl.),5, 715 (1960); Zh. Neors.Khin.,5, 1414(t96O\. 12. Yu- A^Kharitooov,Ni Chia-Chiang,and A. V. Babaeva,Rsss. J. Jnorg. Chen.(Engt.Transl.), 1, 9 \1962);Zh. Neorg. Khi,l...,1,2l(1962). ll. Yu. A- Kharitonov, Ni Tszya-Tzan,,and A. V. Babaeva,proc. Acad. S.,. USSR (Errl. Ttonsl.),l1t, I185 (1961);Dokj. ,4kdd.Nari
