Subgroup 4 (Ti, Zr, Hf) derivatives of Cobalt Carbonyls

Bimetallic and trimetallic compounds containing unsupported bonds of subgroup 4 metals (M = Ti, Zr, Hf) and Co were prepared by hydride elimination (A) from R   4 1 M derivatives (R 1 = PhCH 2 ; R   2 2 N; R 2 = Me, Et)) and by salt elimination (B) from R   3 1 MX (X = Cl, Br; R. 1 = PhCH 2 , R   2 2 N and R 3 O; R 3 = i‐Pr, n‐Bu)) by reaction with HCo(CO) 4 and Na[Co(CO) 4 ], respectively. Compounds R   3 1 MCo(CO) 4 with R 1 = PhCH 2 , R   2 1 M[Co(CO) 4 ] 2 R. 1 = PhCH 2 , were prepared both by methods A and B, while (R 3 O) 4 ‐n Ti[Co(Co) 4 ]n (n = 1, 2) compounds were obtained by reaction B. Several tertiary phosphine and phosphite derivatives of the former two types were obtained by substitution of a carbonyl group by PR   3 4ligand or by A type reaction of HCo(CO) 3 (PR   3 4with R   4 1 M compounds.