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• W2016960495 abstract "The molybdenum and tungsten dinitrogen-organonitrile complexes trans-[M(N2)(NCR)(dppe)2] (2, MMo; 4, MW; RPh, C6H4Me-p, C6H4OMe-p, Me; dppePh2PCH2CH2PPh2) underwent double protonation at the nitrile carbon atom with loss of N2 and a change in oxidation state to +4 on treatment with hydrochloric acid to afford the cationic imido complexes trans-[MCl(NCH2R)(dppe)2]+. The solid-state structure of trans-[WCl(NCH2CH3)(dppe)2][PF6]·CH2Cl2 was determined by single-crystal X-ray analysis. Protonation of complexes 2 by fluoroboric acid or hydrobromic acid also formed the similar imido complexes trans-[MoX(NCH2R)(dppe)2]+ (XF, Br). In contrast, the dinitrogen complex trans-[Mo(N2)2(dppe)2] reacted with two equiv. of benzoylacetonitrile, a nitrile with acidic CH hydrogen atoms, to give the nitrido complex trans-[Mo(N)(NKCCHCOPh)(dppe)2] (12), which was accompanied by evolution of dinitrogen and the formation of 1-phenyl-2-propen-1-one in high yields. For complex 12, the zwitterionic structure, where the anionic enolate ligand PhC(O+)CHCN coordinates to the cationic Mo(IV) center through its nitrogen atom, was confirmed by spectroscopic measurements and single-crystal X-ray analysis. A unique intermolecular aromatic CH⋯O hydrogen bonding was observed in that crystal structure. Complex 12 is considered to be formed via the cleavage of the CN triple bond of benzoylacetonitrile on the metal. A reaction mechanism is proposed, which includes the double protonation of the nitrile carbon atom of the ligating benzoylacetonitrile on a low-valent molybdenum center." @default.
• W2016960495 created "2016-06-24" @default.
• W2016960495 creator A5036717014 @default.
• W2016960495 creator A5042344549 @default.
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• W2016960495 creator A5076833319 @default.
• W2016960495 date "1998-10-01" @default.
• W2016960495 modified "2023-10-18" @default.
• W2016960495 title "Reactivities of the coordinated organonitriles in molybdenum(0) and tungsten(0) phosphine complexes: protonation of the nitrile carbon and cleavage of the CN triple bond" @default.
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• W2016960495 doi "https://doi.org/10.1016/s0020-1693(98)00060-7" @default.
• W2016960495 hasPublicationYear "1998" @default.
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