Reactions of tert-Butyl Isocyanate and Trimethylsilyl Azide with Imidoamido Compounds of Chromium, Molybdenum and Tungsten

DOI: 10.1039/DT9930000781

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 781 - 788 (1993)

Update date:2022-08-03

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Authors:

Lam, Hon-wah

Wilkinson, Geoffrey

Hussain-Bates, Bilquis

Hursthouse, Michael B.

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Article abstract of DOI:10.1039/DT9930000781

tert-Butyl isocyanate and Cr(NBu^t)2(NHBu^t)2 react to form a complex containing the dianion of N,N',N''-tri-tert-butylbiuret Cr(NBu^t)2<tNC(O)>2NBu^t>.The crystal structure of its hydrogen-bonded adduct with t(H)NC(O)>2NBu^t has been determined and the ligand found to bind its three N atoms, whereas in solution the (1)H NMR spectrum indicates a six-membered chromium metallacyclic structure.Interaction of Mo(NBu^t)2(NHBu^t)2 and of Cr(NBu^t)2 with Bu^tNCO, gives (M = Cr, R = C6H3Cl2-2,6; M = Mo, R = Bu^t) confirmed by the crystal structure of the molybdenum compound as having N,O bonding in a four-membered metallacycle.The previously described tungsten analogue has been reformulated as having the same structure.In all these reactions Bu^tNCO is inserted into the M-N bond of the MNHR groups and not into that of the MNR imido groups.The tungsten ureato(1-)-N,O compound reacts with HCl in Et2O to give WCl3(NBu^t)(NHBu^t)t)2> and the crystal structure confirms an octahedral structure with unidentate O-bonded di-tert-butylurea.Interaction of M(NBu^t)2(NHBu^t)2, M = Cr or W, with SiMe3(N3) gives, respectively, the azido species Cr(NBu^t)2(N3)2 and t)2(N3)(NH2Bu^t)>2(μ-N3)2.The structure of the latter has been confirmed by X-ray crystallography.

Full text of DOI:10.1039/DT9930000781

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