Stereoselective oxidative-addition reaction of molecular iodine and mercury(II) halides to rhodium dithiolate compounds. Crystal structure of [Rh2{µ-S(CH2)2S}Cl2(CO)2(PPh3)2]
Abstract
The binuclear complexes [Rh2{µ-S(CH2)2S}(L2)2][L2= cycloocta-1,5-diene (cod)1, L2=(CO)22] and [Rh2{µ-S(CH2)2S}(CO)2(PR3)2](R = Ph 3 or OPh 4) have been prepared and oxidative addition of the electrophiles I2 and HgX2(X = Cl or I) investigated. Compounds 3 and 4 undergo stepwise addition of molecular iodine to yield the symmetrical complexes [Rh2{µ-S(CH2)2S}In(CO)2(PR3)2][n= 2, R = Ph 5, R = OPh 6; n= 4, R = Ph 7, R = OPh 8]. However, interaction of 3 with HgX2(X = Cl or I) affords the unsymmetrical compounds [Rh2{µ-S(CH2)2S}X2(CO)2(PPh3)2](X = Cl 9 or I 10). The crystal structure of 9 has been determined by X-ray diffraction methods.
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