Synthesis and Reactivity of N,N,N’,N’-Tetramethyldiaminomethane (TMDM) Complexes of Tricarbonylrhenium(I). X-Ray Molecular Structures of [ReBr(CO)₃(TMDM)] and [{Re(bipy)(CO)₃}₂(μ-OH)][SbF₆].

Heard, Peter J, Sroisuwan, Phunrawie and Tocher, Derek A (2003) Synthesis and Reactivity of N,N,N’,N’-Tetramethyldiaminomethane (TMDM) Complexes of Tricarbonylrhenium(I). X-Ray Molecular Structures of [ReBr(CO)₃(TMDM)] and [{Re(bipy)(CO)₃}₂(μ-OH)][SbF₆].

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Abstract

N,N,N′,N′-Tetramethyldiaminomethane (TMDM) is known to act as a source of Me₂NCH in carbonyl substitution reactions, but the reaction of TMDM with the neutral halogenopentacarbonylrhenium(I) compounds gave unexpectedly fac-[ReX(CO)₃(TMDM)] (X=Cl, Br or I), in which the intact TMDM ligand acts in a chelating fashion. The complexes are stable both in the solid-state and in solution, but rapidly decompose on dehalogenation, yielding Re metal. Under anaerobic conditions, the reaction of TMDM with [Re(CO)₃(bipy)]⁺also leads to decomposition. In the presence of oxygen the system is stable. Three Re(bipy) containing species were identified in the reaction mixture: [{Re(CO)₃(bipy)}₂(μ-OH)][SbF₆] (1), which was characterised by X-ray crystallography, [{Re(CO)₃(bipy)}₂(μOH)₂][SbF₆]₂(2) and [Re(OH)(CO)₃(bipy)] (3). Graphical Abstract Reaction of neutral [ReX(CO)₅] (X=Cl, Br or I) with N,N,N′,N′-tetramethyldiaminomethane ((TMDM)) gave unexpectedly fac-[ReX(CO)₃(TMDM)] (X=Cl, Br or I), in which the intact TMDM ligand acts in a chelating fashion. Reaction of TMDM with [Re(CO)₃(bipy)]⁺ under aerobic conditions yields three complexes: [{Re(CO)₃(bipy)}₂(μ-OH)][SbF₆] (1), which was characterised by X-ray crystallography, [{Re(CO)₃(bipy)}₂(μOH₂)][SbF₆]₂(2) and [Re(OH)(CO)₃(bipy)] (3).

Item Type: Article
Additional Information: Copyright © 2003 Elsevier. This is the author's final version of the work. The article was originally published in Polyhedron in 2003 by Elsevier. The full published article can be found at http://dx.doi.org/10.1016/S0277-5387(03)00102-5
Keywords: Tricarbonylrhenium (I) complexes, Tetramethyldiaminomethane, Dimethylamine, X-ray crystallography
Divisions: ?? GlyndwrUniversity ??
Depositing User: ULCC Admin
Date Deposited: 05 Oct 2011 09:14
Last Modified: 11 Dec 2017 20:06
URI: http://glyndwr.repository.guildhe.ac.uk/id/eprint/290

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