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

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

doi:10.1039/DT9930000781

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

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

Research output: Journal Publications and Reviews › RGC 22 - Publication in policy or professional journal

45 Citations (Scopus)

Abstract

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{[Bu^tNC(O)]₂NBu ^t}. The crystal structure of its hydrogen-bonded adduct with [Bu^t(H)NC(O)]₂NBu^t 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(NBu^t)₂(NHBu^t)₂ and of Cr(NBu^t)₂[NH(C₆H₃Cl ₂-2,6]₂ with Bu^tNCO, gives gives M[N(Bu^t)C(O)(NHR)]₂-(NBu^t)₂ (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)-[OC(NHBu^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 [W(NBu^t)₂(N₃)(NH₂Bu ^t)]₂(μ-N₃)₂. The structure of the latter has been confirmed by X-ray crystallography.

Original language	English
Pages (from-to)	781-788
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	5
DOIs	https://doi.org/10.1039/DT9930000781
Publication status	Published - 1993
Externally published	Yes

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@article{02fdfbfcb7d24b5daaddf55d6caaefae,

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

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.",

author = "Hon-Wah Lam and Geoffrey Wilkinson and Bilquis Hussain-Bates and Hursthouse, {Michael B.}",

year = "1993",

doi = "10.1039/DT9930000781",

language = "English",

pages = "781--788",

journal = "Journal of the Chemical Society, Dalton Transactions",

issn = "1470-479X",

publisher = "Royal Society of Chemistry",

number = "5",

}

Reactions of tert-butyl isocyanate and trimethylsilyl azide with imidoamido compounds of chromium, molybdenum and tungsten. / Lam, Hon-Wah; Wilkinson, Geoffrey; Hussain-Bates, Bilquis et al.
In: Journal of the Chemical Society, Dalton Transactions, No. 5, 1993, p. 781-788.

Research output: Journal Publications and Reviews › RGC 22 - Publication in policy or professional journal

TY - JOUR

T1 - Reactions of tert-butyl isocyanate and trimethylsilyl azide with imidoamido compounds of chromium, molybdenum and tungsten

AU - Lam, Hon-Wah

AU - Wilkinson, Geoffrey

AU - Hussain-Bates, Bilquis

AU - Hursthouse, Michael B.

PY - 1993

Y1 - 1993

N2 - 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.

AB - 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.

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UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-37049072602&origin=recordpage

U2 - 10.1039/DT9930000781

DO - 10.1039/DT9930000781

M3 - RGC 22 - Publication in policy or professional journal

SN - 1470-479X

SP - 781

EP - 788

JO - Journal of the Chemical Society, Dalton Transactions

JF - Journal of the Chemical Society, Dalton Transactions

IS - 5

ER -

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

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