Chemistry of trivalent cerium and uranium metallocenes: reactions with alcohols and thiols

The trivalent cerium metallocene (Me{sub 3}CC{sub 5}H{sub 4}){sub 3}Ce reacts with alcohols, HOR (R = CHMe{sub 2} or Ph), or thiols, HSR (R = CHMe{sub 2}, or Ph), to give the dimers (Me{sub 3}CC{sub 5}H{sub 4}){sub 4}Ce{sub 2} ({mu}-ER){sub 2} as shown by X-ray crystallography for the isopropoxide and isopropylthiolate derivatives. Crystals of (Me{sub 3}CC{sub 5}H{sub 4}){sub 4}Ce{sub 2}({mu}-OCHMe{sub 2}){sub 2} are monoclinic, P2{sub 1}/c with a = 11.962 (4) {angstrom}, b = 14.489 (5) {angstrom}, c = 12.384 (5) {angstrom}, {beta} = 103.31 (3){degree}, and V = 2,089 {angstrom}{sup 3}; the structure was refined by full-matrix least-squares methods to a conventional R factor for 0.028, 2,874 data, F{sup 2} > 2{sigma}(F{sup 2}). Crystals of (Me{sub 3}CC{sub 5}H{sub 4}){sub 4}Ce{sub 2}({mu}-SCHMe{sub 2}){sub 2} are also monoclinic, P2{sub 1}/n with a = 14.255 (9) {angstrom}, b = 13.585 (9) {angstrom}, c = 11.265 (7) {angstrom}, {beta} = 96.02 (5){degree}, V = 2,170 {angstrom}{sup 3}. The uranium metallocene (Me{sub 3}CC{sub 5}H{sub 4}){sub f3}U reacts with HSPh at low temperature to give isolable (Me{sub 3}CC{sub 5}H{sub 4}){sub 3}USPh and unidentified material.