Reactions of tert-butyl isocyanate and trimethylsilyl azide with imidoamido compounds of chromium, molybdenum and tungsten

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)22_Publication in policy or professional journal

37 Scopus Citations
View graph of relations

Author(s)

  • Hon-Wah Lam
  • Geoffrey Wilkinson
  • Bilquis Hussain-Bates
  • Michael B. Hursthouse

Detail(s)

Original languageEnglish
Pages (from-to)781-788
Journal / PublicationJournal of the Chemical Society, Dalton Transactions
Issue number5
Publication statusPublished - 1993
Externally publishedYes

Abstract

tert-Butyl isocyanate and Cr(NBut)2(NHBut)2 react to form a complex containing the dianion of N,N′,N″ -tri-tert-butylbiuret Cr(NBut)2{[ButNC(O)]2NBu t}. The crystal structure of its hydrogen-bonded adduct with [But(H)NC(O)]2NBut has been determined and the ligand found to bind its three N atoms, whereas in solution the 1H NMR spectrum indicates a six-membered chromium metallacyclic structure. Interaction of Mo(NBut)2(NHBut)2 and of Cr(NBut)2[NH(C6H3Cl 2-2,6]2 with ButNCO, gives gives M[N(But)C(O)(NHR)]2-(NBut)2 (M = Cr, R = C6H3Cl2-2,6; M = Mo, R = But) 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 ButNCO 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(NBut) (NHBut)-[OC(NHBut)2] and the crystal structure confirms an octahedral structure with unidentate O-bonded di-tert-butylurea. Interaction of M(NBut)2(NHBut)2, M = Cr or W, with SiMe3(N3) gives, respectively, the azido species Cr(NBut)2(N3)2 and [W(NBut)2(N3)(NH2Bu t)]2(μ-N3)2. The structure of the latter has been confirmed by X-ray crystallography.

Citation Format(s)

Reactions of tert-butyl isocyanate and trimethylsilyl azide with imidoamido compounds of chromium, molybdenum and tungsten. / Lam, Hon-Wah; Wilkinson, Geoffrey; Hussain-Bates, Bilquis; Hursthouse, Michael B.

In: Journal of the Chemical Society, Dalton Transactions, No. 5, 1993, p. 781-788.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)22_Publication in policy or professional journal