CHEMISTRY OF MOLYBDENUM COMPLEXES WITH (TRIPHENYLMETHYL)ALLENE

The cationic allene complex [Mo(eta(5)-C5H5)(CO)(3)(eta(2)-CH2=C=CHCPh (3))]BF4 1, was converted into the dihydronaphthyl complex [Mo(eta(5)- C5H5)(CO)(3)(C(10)H(7)Ph(2))] in the presence of KSCN as the major pro duct. When the reaction was carried out at high concentration, the all ylic complex [Mo(eta(5)-C5H5) (CO)(2){eta(3)-CH2C(COC(10)H(7)Ph(2))CHC Ph(3)}] was isolated as a minor product. Reaction of allene with the d ihydronaphthyl complex also induced insertion of CO followed by C-C co upling to give the allylic complex )-C5H5)(CO)(2){eta(3)-CH2C(COC(10)H (7)Ph(2))CH2}]. In CH CI, migration of the organic moiety on Mo in the dihydronaphthyl to the C5H5 ligand occurred giving [MoCl{eta(5)-C5H4( C(10)H(7)Ph(2))}(CO)(3)]. In tetrahydrofuran and MeCN, similar reactio ns gave [MoH{eta(5)-C5H4(C(10)H(7)Ph(2))}(CO)(3)] and C5H5(C(10)H(7)Ph (2)) respectively. Under thermolytic conditions o(eta(5)-C5H5)(CO)(2)( PPh(3))(C(O)C(10)H(7)Ph(2))] was also converted into MoCl{eta(5)-C5H4( C(10)H(7)Ph(2))}(CO)(2)(PPh(3))]. The latter complex and [W(eta(5)-C5H 5)(CO)(3)(C(10)H(7)Ph(2))] have been characterized by X-ray diffractio n analysis.