The trivalent cerium metallocene, (Me3CCsH4)3Ce, reacts with alcohols, HOR (R = CHMe2 or Ph), or thiols, HSR (R = CHMe2, or Ph), to give the dimers (Me3CCsl4)4Ce2 (~-ER)2 as shown by X-ray crystallography for the isopropoxide and isopropylthiolate derivatives.Crystals of (Me3CCsH4)4Ce2 ~-OCHMe2h are monoclinic, P2t/c with a= 11.962(4) A, b = 14.489(5)A, c = 12.384(5) A, J3 = 103.31(3)0 , and V = 2089 A3; the structure was refined by full-matrix least squares to a conventional R-factor of 0.028, 2874 data, F2 > 2a(F2).The Ce2~ unit is planar and the geometry about the cerium atom is pseudotetrahedral and the geometry is planar about the oxygen atom.Crystals of (Me3CCsH4)4Ce2 (~-SCHMe2h are also monoclinic, P2t/n with a= 14.255(9) A, b = 13.585(9)A, c = 11.265(7)A, J3 = 96.02(5)0, v =2170 A3; the structure was refmed by full-matrix least squares to a conventional R-factor of 0.028, 2899 data,
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Stults et al. (1990) studied this question.