2924Organometallics,Vol.29,No.13,2010andphenylene).31P{1H}NMR((CD3)2CO,121.5MHz):δ(ppm)-144.7825.58(septet,(s,CPPPh3),20.64(s,CPPh3),-1.482JF(s,OsPPh3),(PC)6).13C{1H}NMR((CD=15.1Hz,OsCH),3)240.352CO,75.5MHz):δ(ppm)254.70(d,(d,2J(PC)=15.1Hz,OsCH),153.74(t,2J(PC)=21.9Hz,OsCHC(PPhCH),143.15(s,CtN),118.47-135.47(m,PPh3)-J(PC)=71.9Hz,OsCHC(PPh3andphenylene),115.36(d,1(PPh3)),114.40(d,1J(PC)=70.1Hz,OsCHCforC3)).IR(cm-1):νCtN=2095cm-1.Anal.Calcd132H104Cl4F12N2P8Os2:C,58.37;H,3.86;N,1.03.Found:C,58.25;H,4.23;N,1.13.

[μ-(4,40-Diisocyanodiphenylmethane){Os(CHC(PPh)CH)Cl][PF3)CHC-(PPh32(PPh3)}2,complex6]2(5b).Bythesamemethodasthatforthepreparationof5a5bwasobtainedasagreensolidfromthereactionof3(0.31g,0.22mmol)with4,40-diisocyano-diphenylmethane(4b)(24mg,0.11mmol)indichloromethane(30mL)inthepresenceofNH4PF6(37mg,0.22mmol).Yield:0.213

g,68%.1HNMR(CD2Cl2,300.1MHz):δ(ppm)17.45(d,J(PH)=18.9Hz,2H,OsCH),15.74(d,3J(PH)=24.9Hz,2H,OsCH),8.33(t,3J(PH)=14.4Hz,2H,OsCHC(PPh3)CH),6.39-7.99(m,98H,PPh3andphenylene),3.81(s,CH2).31P{1H}NMR(CD2Cl2,121.5MHz):δ(ppm)24.88(s,CPPh3),19.74(s,CPPh3),-1.20(s,OsPPh3),-144.75(septet,PF6).13C{1H}NMR(CD2Cl2,75.5MHz):δ(ppm)253.76(d,2J(PC)=15.2Hz,OsCH),238.03(d,2J(PC)=15.5Hz,OsCH),152.76(t,2J(PC)=21.8Hz,OsCHC(PPh3)CH),143.341(s,CtN),117.46-136.78(m,PPh3andphenylene),116.86(d,J(PC)=75.6Hz,OsCHC-(PPh3)),115.46(d,1J(PC)=70.6Hz,OsCH(CPPh3)),41.36(s,CH2).IR(cm-1):νCtN=2109cm-1.Anal.CalcdforC133H106-Cl4F12N2P8Os2:C,58.51;H,3.91;N,1.03.Found:C,58.32;H,3.61;N,1.09.

[μ-(Bis(4-isocyanophenyl)ether){Os(CHC(PPhCl)}3)CHC(PPh3)-CH)2(PPhof35a2][PF,complex6]2(5c).Bythesamemethodasthatforthepreparation5cwasobtainedasagreensolidfromthereactionof3(0.36g,0.26mmol)withbis(4-isocyanophenyl)ether(4c)(28mg,0.13mmol)indichloromethane(35mL)inthe1

presenceofNH4PF6(44mg,0.27mmol),Yield:0.21g,58%.HNMR((CD3)2CO,400.1MHz):δ(ppm)16.36(d,3J(PH)=19.6Hz,2H,OsCH),14.62(d,3J(PH)=25.2Hz,2H,OsCH),7.98(t,3J(PH)=13.2Hz,2H,OsCHC(PPhH,PPh3)CH),6.81-7.98(m,983andphenylene).31P{1H}NMR((CD25.48(s,CPPhPPh3)2CO,162.0MHz):δ(ppm)3),20.59(s,CC{1H}NMR((CD3),-1.83(s,OsPPhMHz):3),-144.22(septet,PFδ(ppm)259.75(d,6).132J(PC)=15.4Hz,Os3)2CO,100.6CH),245.35(d,2J(PC)=15.9Hz,OsCH),158.91(t,2J(PC)=21.9Hz,OsCHC(PPhandphenylene),3)CH),145.15(s,CtN),120.21-140.61(m,PPh120.41(d,1J(PC)=70.9Hz,OsCHC(PPh3119.72(d,1J(PC)=70.5Hz,OsCHC(PPh3)),cm-1.Anal.CalcdforC3)).IR(cm-1):νCtN=2081H,3.84;N,1.03.Found:C,58.24;132H104ClH,4.04;4F12NN,2OP1.05.

8Os2:C,58.02;[μ-(1,4-Phenylenediisocyanide){Os(CHC(PPhPPh3)CHC(PPhCH)Cl3)-2(3)}2][PF6]2(5d).Bythesamemethodasthatforthepreparationof5a,complex5dwasobtainedasagreensolidfromthereactionof3(0.25g,0.18mmol)with1,4-phenylene-diisocyanide(4d)(12mg,0.09mmol)indichloromethane(25mL)inthepresenceofNH4PF6(30mg,0.18mmol).Yield:0.18g,78%.13

HNMR((CD3)2CO,300.1MHz):δ(ppm)16.45(d,J(PH)=18.9Hz,2H,OsCH),14.54(d,3J(PH)=23.7Hz,2H,OsCH),7.95(t,3J(PH)=12.6Hz,2H,OsCHC(PPh7.82(m,94H,PPh1H}3)CH),6.14-3andphenylene).31P{NMR((CD3)2CO,121.5MHz):δ(ppm)25.36(s,CPPh3),20.65(s,CPPh3),-1.47(s,OsPPh3),-144.56(septet,PF6).13C{1H}NMR((CD3)2CO,75.5MHz):δ(ppm)253.67(d,2J(PC)=215.3Hz,OsCH),240.12(d,2J(PC)=15.4Hz,OsCH),152.89(t,J(PC)=21.9Hz,OsCHC(PPhPPh3)CH),144.06(s,CtN),118.65-135.45(m,3andphenylene),1116.11(d,1J(PC)=70.8Hz,OsCHC-(PPhν3)),114.32(d,J(PC)=70.8Hz,OsCHC(PPh=2088cm-1.Anal.CalcdforC3)).IR(cm-1):CtN126H100Cl4F12N2P1.06.Found:C,57.43;H,4.16;N,0.85.

8Os2:C,57.32;H,3.82;N,[μ-(1,4-Phenylenediisocyanide){Os(CHC(PPh3)C(OEt)O)Cl-(PPh3)2}2Cl2(7).Amixtureofcomplex6(0.20g,0.18mmol),

Huangetal.

1,4-phenylenediisocyanide(4d)(11mg,0.09mmol),andNHmg,0.35mmol)inCH4PF(586htogivea2Clbrown2(30mL)wasstirredatroomtemperaturefor10suspension.Evaporationofthesolventgaveasolid,whichwaspurifiedbycolumnchromato-graphy(neutralalumina,solvent:dichloromethane,eluent:dichloromethane/methanol,20:0.3).Theyellowbandwascollected,evaporatedtodryness,andrecrystallizedfromdichloromethaneanddiethyl1ethertogiveabrightyellowpowderof7.Yield:0.17g,78%.HNMR(CDCl3,400.1MHz):δ(ppm)12.73(d,3J(PH))=12.4Hz,2H,OsCH),6.81-7.70(m,94H,PPh31(m,4H,OCHHz,3andphenylene),3.982),0.50(t,3J(HH))=7.26H,OCH162.0MHz):δ(ppm)14.83(s,C2CHPPh3).P{1

H}NMR(CDCl(s,OsPPh).13C{3,1H}NMR(CDCl3),10.23H),3181.50(d,2J(PC)=16.43,100.6MHz):δ(ppm)239.51(m,OsCHz,C(OCHCtN),98.81(d,1J(PC)=73.4Hz,CPPh2CH3)),145.73(s,135.00(m,PPh3),114.88-CH3andphenylene),64.41(s,OCH2),13.50(s,OCH23).Anal.CalcdforC126H106O2N2P6ClN,1.16.Found:C,62.74;H,4.66;N,1.05.

4Os2:C,62.53;H,4.41;[μ-(4,40-Biphenyldiisocyanide){Os(CHC(PPhflaskwascharged3)CHCClCH)Cl-(PPh3)2}2]Cl2(9a).ASchlenkwithcomplex8(0.43g,0.38mmol),4,40-biphenyldiisocyanide(4a)(39mg,0.19mmol),NH4PF6(63mg,0.38mmol),NaCl(0.11g,1.91mmol),anddegassedCH2Cl2(30mL).Themixturewasheatedunderrefluxfor3handthenallowedtocoolbeforebeingfilteredthroughCelite.Evaporationofthesolutiongaveasolid,whichwaspurifiedbycolumnchromatography(neutralalumina,sol-vent:dichloromethane,eluent:dichloromethane/acetone,3:1).Thegreenbandwascollected,evaporatedtodryness,andrecrys-tallizedfromdichloromethaneanddiethylethertogiveagreenishpowderδofH,(ppm)OsCH16.629a.Yield:CPPh(s,2H,0.32OsCg,H65%.1CCl),H13.73NMR(d,(CD32Cl2,300.1MHz):J(PH)=27.9Hz,23),7.79(d,3J(PH)=13.1Hz,2H,OsCHCClCH),6.30-7.57(m,98H,PPh3andphenylene).31P{1H}NMR(CD2Cl2,121.5MHz):δ(ppm)18.68(s,CPPh3),-3.34(s,OsPPh3).13C{1H}NMR(CD2Cl2,75.5MHz):δ(ppm)251.94(s,OsCHCCl),233.40(br,OsCHCPPh3),153.18(s,CtN),139.47(d,2J(PC)=22.4Hz,OsCHCClCH),136.53(d,3J(PC)=15.5Hz,OsCH1CCl),126.22-135.05(m,PPh3andphenylene),115.48(d,J(PC)=72.5Hz,OsCHC(PPh3)).IR(cm-1):νCtN=2084cm-1.Anal.CalcdforC132H104Cl6N2P6Os2:C,63.49;H,4.20;N,1.12.Found:C,63.74;H,4.26;N,1.05.

[μ-(4,40-Diisocyanodiphenylmethane){Os(CHC(PPh)Cl(PPh9b).Bythesamemethodasthat3)CHC-ClCH3)2}2]Cl2(forthepreparationof9a,complex9bwasobtainedasagreensolidfromthereactionof8(0.34g,0.28mmol)with4,40-diisocyanodiphe-nylmethane(4b)(32mg,0.15mmol)indichloromethane(35mL)inthepresenceofNaCl(87mg,1.49mmol)andNH4PF0.28δ(ppm)mmol).16.68Yield:(s,20.21H,7.82OsCg,54%.16(45mg,(d,HCCl),HNMR3J(PH)13.77=13.4(d,(CD3J2Cl(PH)2,400.1MHz):=27.9Hz,2H,OsCHCPPh3),Hz,2H,OsCHC-ClC31

H),6.38-7.59(m,98H,PPh3andphenylene),3.98(s,CH2).-P{13.01H}(s,NMROsPPh(CD2Cl2,162.0MHz):δ(ppm)18.57(s,CPPh100.6MHz):3),3).13C{1H}NMR(CD2Cl2,δ(ppm)265.09(s,OsCHCCl),232.45(br,OsCHCPPh(s,C3tN),139.69(d,2J(PC)=22.1Hz,OsCHCClCH),3),141.78136.38(d,J(PC)=13.1Hz,OsCHCCl),125.88-134.89(m,PPhandphenylene),115.36(d,1J(PC)=72.7Hz,OsCHC(PPh33)),42.12(s,CH2).IR(cm-1):ν63.61;CtN=2086cm-1.Anal.CalcdforC133H106Cl6N2P6Os2:C,H,4.25;N,1.12.Found:C,63.73;H,4.72;N,1.03.

[μ-(Bis(4-isocyanophenyl)ether){Os(CHC(PPh3)CHCClCH)-Cl(PPh3)2}2]Cl2(9c).Bythesamemethodasthatforthepre-parationof9a,complex9cwasobtainedasagreensolidfromthereactionof8(0.35g,0.31mmol)withbis(4-isocyanophe-nyl)ether(4c)(34mg,0.15mmol)indichloromethane(35mL)inthepresenceofNaCl(0.12g,1.98mmol)andNH4PFδ(ppm)mmol).16.62Yield:(s,2H,0.18OsCg,47%.1HCCl),H13.67NMR(d,(CDCl6(52mg,0.323J(PH)3,400.1MHz):=30.4Hz,2H,OsCHCPPh3),7.56(d,3J(PH)=13.2Hz,2H,OsCHCClCH),6.23-7.36(m,98H,PPh3andphenylene).31P{1H}NMR