New J. Chem. 2009, 33, 1320-1323(4)

Found:C,54.80;H,4.70;N,2.30%.HRMS:m/z=573.1069[M]+(calc.forC26H25F6N1S2Si=573.1051).Preparationof1(o,o)

ToaTHFsolutionof6(350mg,0.64mmol)and7(126mg,0.28mmol)wasaddedt-BuOK(77mg,0.70mmol).Afterre uxingovernight,thereactionmixturewashydrolyzedwithwater,andtheorganicphasewashedwithasaturatedsolutionofNa2CO3,driedoverMgSO4andevaporatedinvacuo.TheresiduewasrecrystallizedfromaCH2Cl2/pentanemixtureatÀ201Ctogive1(o,o)asaredpowder(180mg,50%).1HNMR(500MHz,CDCl3):d8.63(d,3J=5.1Hz,1H,Py6),8.26(s,1H,Py3),7.53(d,3J=8.9Hz,2H,C6H4),7.25(s,1H,thio),7.23(s,1H,thio),7.17(dd,3J=5.1Hzand4

J=1.6Hz,1H,Py5),6.94(d,3J=15.9Hz,1H,QCH),6.77(d,3J=8.9Hz,2H,C6H4),6.71(d,3J=15.9Hz,1H,QCH),3.05(s,6H,NMe2),1.99(s,3H,Me)and0.03(s,9H,TMS).131

C[H]NMR(125MHz,CDCl3):d156.4,150.7,149.4,147.8,147.5,146.2,144.7,139.5,138.5,133.5,128.4,126.9,126.5,125.6,123.5,120.9,120.7,119.6,119.0,112.3,40.3,14.5andÀ0.6.Anal.calc.forC64H58F12N4S4Si2:C,59.33;H,4.51;N,4.32.Found:C,59.87;H,4.86;N,4.79%.HRMS:m/z=1294.2875[M]+(calc.forC64H58F12N4Si2S4=1294.2891).Spectroscopiccharacterizationof1(c,o)

Compound1(c,o)wasgeneratedbytheirradiation(l=436nm)ofad12-cyclohexanesolutionof1(o,o)for30min.Selecteddata:1

HNMR(500MHz,d12-cyclohexane):d8.48and8.46(2Âd,3

J=5Hz,2H,Py6),8.49and8.42(2Âs,2H,Py3),7.58(d,3

J=15.7Hz,1H,QCH(c)),7.25(s,1H,thio(o)),7.21(s,1H,thio(o)),7.09and6.95(2Âdd,3J=5.1Hz,2H,Py5),6.92(d,3

J=15.9Hz,1H,QCH(o)),6.70(s,1H,thio(c)),6.33(s,1H,thio(c)),2.97and2.96(2Âs,12H,NMe2),and2.04and1.96(2Âs,6H,Me).

X-Raydi ractionstudyof1(o,o)

SinglecrystalsforX-raydi ractionstudiesweregrownbytheslowevaporationofaCH2Cl2solutionofcomplex1(o,o)at201C.Thesample(0.32Â0.28Â0.28mm)wasstudiedonanOxfordDi ractionXcaliburSaphir3di ractometerwithgraphitemonochromatizedMo-Karadiation.C64H58F12N4S4Si2,M=1295.6,monoclinic,P21/n,a=10.45582(5),

,b=100.277(4)1,b=19.8097(9),c=14.9154(7)A

3,Z=2,rcalc=1.415gcmÀ3,mMo-K=V=3040.5(2)Aa

2.77mmÀ1,re ectionscollected=21731,independent

re ections=6585,independentre ectionswithI42s(I)=4381,R1(alldata)=0.1086andwR2(alldata)=0.2618.w

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