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• W1970236946 endingPage "2275" @default.
• W1970236946 startingPage "2263" @default.
• W1970236946 abstract "The metalate salts Y+[Cp‘M(CO)2(CNR)]- (Y = Na, K; M = Mo, W; CNR = alkylisocyanide), in the presence of the soft electrophile MeI, experience alkylation at the metal center to afford methyl complexes of composition Cp‘MMe(CO)2(CNR). The kinetic stability of these alkyls toward rearrangement to the η2-iminoacyls Cp‘M(η2-C(NR)Me)(CO)2 or the η3-1-azaallyls Cp‘M(η3-CH2C(H)NR)(CO)2 has been found to depend markedly upon the nature of the metal, the isocyanide R substituent, and the solvent used. With respect to the latter, solvents with efficient Lewis basic capabilities (e.g., pyridine or acetonitrile) favor η2-iminoacyl formation while those which are poor donors (benzene, diethyl ether) preferentially generate the η3-azaallyls. The use of acetone as the solvent in reactions involving the Me−W−CNR complexes has allowed the isolation of metallacyclic structures of composition Cp‘W(η2(C,O)-C(Me)N(R)C(Me)2O)(CO)2, formally as the result of a [3 + 2] cycloaddition of a W−η1-C(NR)Me residue to a molecule of acetone. Two of the newly reported complexes, namely the η3-1-azaallyl CpMo(η3-CH2CHN-t-Bu)(CO)2 (1az) and the heterometallacycle CpW(η2(C,O)-C(Me)N(Me)C(Me)2O)(CO)2 (9cad) have been structurally characterized by X-ray crystallography." @default.
• W1970236946 created "2016-06-24" @default.
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• W1970236946 date "1997-05-01" @default.
• W1970236946 modified "2023-10-03" @default.
• W1970236946 title "Formation of η²-Iminoacyls, η³-Azaallyls, and Heterometallacycles during the Rearrangements of Methyl Complexes of Molybdenum and Tungsten Containing Isocyanide Ligands" @default.
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• W1970236946 doi "https://doi.org/10.1021/om970109o" @default.
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