Organometallics 2010, 29, 2916–2925电化学(10)

Article

Table3.CrystalDataandStructureRefinementfor9d

9d32CH2Cl234H2O

empiricalformulaC126H100Cl8N2Os2P6fw

2733.8232CH2Cl234H2Otemperature,K

173(2)radiation(MoKR),A

0.71073crystsysttriclinicspacePa,Agroup13.2136(4)b,A13.7646(4)c,A18.1729(6)Rβ,deg103.599(3)γ,deg99.835(3)V,,deg

A395.375(2)3134.34(17)Z

1dcalcd,gcm-31.448F(000)

1372

crystsize,mm30.2Â0.2Â0.05θreflnsrange,collecteddeg2.3527768-25.00indepreflns

10764obsdreflns(I>2σ(I))8964

data/restraints/params10764/60/704goodness-of-fitonF21.000

finalR(I>2σ(I))R1=0.0368,wR2=0.0927Rindices(alldata)

R1=0.0487,wR2=0.0955

(CDCl3,162.0MHz):δ(ppm)17.00(s,CPPh).13C{1H}NMR(CDCl3),-5.18(s,OsPPh33,100.6MHz):δ(ppm)251.70(s,Os2

CHCCl),233.16(br,OsCHCPPhH),3),156.22(s,CtN),139.28(d,J(PC)=22.1Hz,OsCHCClC136.42(d,3J(PC)=11.5Hz,OsCH1CCl),126.20-135.01(m,PPh3andphenylene),115.35(d,J(PC)-1=72.6Hz,OsCHC(PPh.Anal.CalcdforC3)).IR(cm-1):νCtN=2075cm132H104Cl6N2OP6Os2:C,63.08;H,4.17;N,1.11.Found:C,63.34;H,4.38;N,1.08.

[μ-(1,4-Phenylenediisocyanide){Os(CHC(PPh9d).Bythesamemethodasthat3)CHCClCH)-Cl(PPh3)2}2]Cl2(forthepre-parationof9a,complex9dwasobtainedasagreensolidfromthereactionof8(0.32g,0.28mmol)with1,4-phenylenediisocyanide(4d)(18mg,0.14mmol)indichloromethane(30mL)inthepresenceofNaCl(82mg,1.40mmol)andNH0.23g,67%.1HNMR(CD4PF6(45mg,0.28mmol).Yield:2Cl2,300.1MHz):δ

Organometallics,Vol.29,No.13,20102925

(ppm)16.52(s,2H,OsCHCCl),13.63(d,3J(PH)=28.5Hz,2H,OsCHCPPh3),7.83(d,3J(PH)=13.6Hz,2H,OsCHCClCH),6.01-7.63(m,94H,PPh3andphenylene).31P{1H}NMR(CD13

,121.51MHz):δ(ppm)18.67(s,CPPh2.12(s,OsPPh2-Cl23),-3).C{H}NMR(CDHCCl),2Cl2,75.5MHz):δ(ppm)251.89(s,OsC-2

233.01(br,OsCHCPPh3),156.21(s,CtN),139.58(d,J(PC)=22.7Hz,OsCHCClCH),136.34(d,3J(PC)=12.8Hz,OsCHCCl),126.32-135.17(m,PPh(d,1J(PC)=74.8Hz,OsCHC(PPh3andphenylene),116.04cm-1.Anal.CalcdforCN3)).IR(cm-1):νCtN=2064Found:C,62.39;H,126H4.22;100ClN,61.13.

2P6Os2:C,62.50;H,4.16;N,1.16.X-rayCrystalStructuresDeterminationof9d.Datacollec-tionswereperformedonanOxfordGeminiSUltraCCDareadetectorusing(λ=0.71073A

graphite-monochromatedMoKRradiation

)at173K.Multiscanorempiricalabsorptioncorrections(SADABS)wereapplied.Allstructuresweresolvedbydirectmethods,expandedbydifferenceFouriersyntheses,DC-745238(9d)dc.cam.ac.uk/data_request/cif.Detailsoncrystaldata,datacollection,andrefinementsaresummarizedinTable3.

Acknowledgment.ThisworkwasfinanciallysupportedbytheNationalScienceFoundationofChina(Nos.20925208,20872123,and20772100),theProgramforNewCenturyExcellentTalentsinUniversityofChina(NCET-08-0471),theProgramforNewCenturyExcellentTalentsinFujianProvinceUniversity,andtheYoungTalentProjectoftheDepartmentofScience&TechnologyofFujianProvince(2007F3095).

SupportingInformationAvailable:X-raycrystallographicfiles(CIF).ThesematerialsareavailablefreeofchargeviatheInternetat.