1224571-68-9Relevant articles and documents
Chemistry of unsaturated group 6 metal complexes with bridging hydroxy and methoxycarbyne ligands. 6. C-E bond formation and C-O bond cleavage processes in the reactions of [Mo2(η5-C5H 5)2(μ-COMe)(μ-PCy2)(μ-CO)] with several p -block elements (E) and their hydride derivatives
Esther Garcia,Garcia-Vivo, Daniel,Ruiz, Miguel A.
, p. 2157 - 2165 (2010/07/04)
The unsaturated complex [Mo2Cp2(μ-COMe)(μ- PCy2)(μ-CO)] (1) reacts with several HERn molecules (HERn = HSPh, HPHPh, HSnPh3) in toluene at 263-288 K to give the corresponding derivatives [Mo2Cp2(μ-ER n)(μ-PCy2)(CO)2]. A related reaction takes place in toluene at 263 K with the diphosphite (EtO)2POP(OEt) 2 to give a mixture of the diethoxyphosphide derivatives [Mo 2Cp2(μ-PCy2){μ-P(OEt)2}(CO) 2] and [Mo2Cp(η5-C5H 4CH2Ph)(μ-PCy2){μ-P(OEt) 2}(CO)2], the latter incorporating a benzyl group from the solvent, and with iodine (in dichloromethane at room temperature) to give first the iodide complex [Mo2Cp2(μ-I)(μ-PCy 2)(CO)2] and then the triiodide derivative [Mo 2Cp2(μ-I)I2(μ-PCy2)(CO) 2]. In all of the above reactions, neat demethylation of the methoxycarbyne ligand takes place. In contrast, the silanes HSiPh3 and H2SiPh2 (unreactive toward 1 in refluxing toluene) react slowly under visible-UV irradiation at room temperature to give in good yields the novel complexes [Mo2Cp2{μ-C(2-C 6H4SiPh2OMe)}(μ-PCy2)(μ-CO)] and [Mo2Cp2(μ-CSiPh2OMe)(μ-PCy 2)(μ-CO)], having arylcarbyne and silylcarbyne ligands, respectively, the latter resulting from the overall elimination of H2 and insertion of Ph2SiC6H4 and SiPh 2 fragments, respectively, into the strong C-OMe bond of the carbyne ligand. The reactions of 1 with elemental selenium and sulfur involve the incorporation of three to four chalcogen atoms to the dimetal center under mild conditions, to give respectively the carbene-seleniolate derivative [Mo 2Cp2{μ-C(OMe)C(O)Se}(μ-PCy2)(μ-Se 2)] and the O-methyldithiocarbonate [Mo2Cp 2(μ-PCy2){μ-S2C(OMe)}(S)2], the latter derived from an unexpected coupling of two sulfur atoms to the carbyne ligand.
