140658-86-2Relevant academic research and scientific papers
Synthesis and reactions of ynol ester complexes of molybdenum and tungsten: Cleavage of the RCCO-C(O)R′ bond and of the RCC-OC(O)R′ bond of ynol ester ligands
Belsky, Kimberly A.,Asaro, Marianna F.,Chen, Sylvia Y.,Mayr, Andreas
, p. 1926 - 1936 (1992)
Reaction of the ketenyl complexes NEt4[M(η2-RCCO) (S2CNR″2)2(CO)] (3, M = Mo, R = Ph, R″ = Et; 4, M = W, R = Ph, R″ = Et (a), R = C6H4CMe3-4, R″ = Et (b), R = Ph, R″ = Me (c)) and K[W(η2-4-Me3C-C6H4CCO)(N 2C6H7)2(CO)] (5) with acyl halides R′COCl (or R′COBr) affords the (ynol ester)metal complexes [M(S2CNR″)2(CO)(η2-RCCOCOR′)] (8: M = Mo, R = Ph, R′ = Ph, R″ = Et) (9: M = W, R = Ph, R′ = Me (a), Ph (b), CHCH2 (c), trans-CHCHMe (d), trans-CHCHPh (e), R″ = Et; R = C6H4CMe3-4, R′ = Me (f), CH2Ph (g), CMe3 (h), R″ = Et; R = Ph, R′ = CMe3, R″ = Me (i)) and [W(N2C6H7)2-(CO)(η 2-4-Me3C-C6H4CCOCOR′)] (10: R = C6H4CMe3-4, R′ = CMe3 (a), CH2Ph (b), C6H4-OMe-4 (c)). Reaction of the ynol ester complexes [W(S2CNEt2)2(CO)(η2-4-Me 3C-C6H4CCOCOCH2R)] (R = H (9f), Ph (9g)) with dimethylamine affords the ketenyl complex [H2NMe2] [W(η2-4-Me3C-C6H4CCO)(S 2CNEt2)2(CO)]. The ynol ester complexes [W(LL)2(CO)(η2-4-Me3C-C6H 4CCOCOCH2Ph)] (LL = S2CNEt2 (9g), N2C6H7 (10b)) react with NaN(SiMe3]2 to give the ketenyl complexes Na[W(η2-4-Me3C-C6H4CCO)(LL) 2(CO)]. Reaction of [W(S2CNEt2)2(η2-4-Me 3C-C6H4CCOCOCMe3)(CO)] (9h) with HNMe2 gives [W(S2CNEt2)2-(η2-4-Me 3C-C6H4CCNMe2)(CO)] (11). Reaction of 9h with PMe3 gives [W(S2CNEt2)2(η2-4-Me 3C-C6H4CCSCSNEt2)(CO)][Me 3CO2] (12). The reaction of 4b with PMe3 affords [W(η2-4-Me3C-C6H4CCO)(S 2CNEt2)(CO)(PMe3)2] (13). The (ynol ether)metal complexes [M(S2CNEt2)2(CO)(η2-RCCOMe)] (6, M = Mo, R = Ph; 7, M = W, R = C6H4CMe3-4) were prepared by reaction of NEt4[M(η2-RCCO)(S2CNR″ 2)2(CO)] with CF3SO3CH3.
