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Synthesis and Reactions of d0 Imido Aryl Derivatives of Chromium, Molybdenum, and Tungsten. Crystal Structures of Cr(NBut)2(C6H2Me3-2,4,6)2, Mo(NBut)2(C6H3Me2-2,6)2, and Cr(NBut)2t>(C6H2Me3-2,4,6)

DOI: 10.1039/DT9880000053

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 53 - 60 (1988)

Update date:2022-08-02

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Authors:

Sullivan, Alice C.Sullivan, Alice C.

Wilkinson, GeoffreyWilkinson, Geoffrey

Motevalli, MajidMotevalli, Majid

Hursthouse, Michael B.Hursthouse, Michael B.

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Article abstract of DOI:10.1039/DT9880000053

The compounds M(NBut)2R'2 (M=Cr, Mo, or W, R'=C6H2Me3-2,4,6 or C6H3Me2-2,6; M=Mo, R'=C6H4Me-o) have been prepared from M(NBut)2(OSiR3)2 (M=Cr, or Mo, R=Me; M=W, R=Ph) and appropriate Grignard reagents.Cr(NBut)2(C6H2Me3-2,4,6)2 reacts with CO to give a thermally unstable bis(acyl)complex Cr(NBut)2(COC6H2Me3-2,4,6)2 which eliminates the amide HN(But)(COC6H2Me3-2,4,6) possibly via acyl migration to the imido nitrogen.Cyclic voltammetry on Cr(NBut)2(C6H2Me3-2,4,6)2 shows a quasi-reversible one-electron reduction, E1/2red=-1.31 V.Reaction of compounds M(NBut)2R'2 (M=Cr, Mo, or W, R'=C6H2Me3-2,4,6; M=Mo, R'=C6H3Me2-2,6) with t-butyl isocyanide gives the corresponding η2-iminoacyls, M(NBut)2t>R'.The X-ray crystal structures of Cr(NBut)2(C6H2Me3-2,4,6)2, Mo(NBut)2(C6H3Me2-2,6)2, and Cr(NBut)2t>(C6H2Me3-2,4,6) have been determined.The first two consist of monomeric distorted tetrahedra in which one o-methyl group on each aryl ligand is positioned close to the metal atom.In the latter compound the structure is best described in terms of a distorted tetrahedron, with the η2-iminoacyl occupying one split site.

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