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Heard, Peter J; Sroisuwan, Phunrawie; Tocher, Derek A
Publisher: Glyndŵr University Research Online
Languages: English
Types: Article
Subjects: Chemistry, X-ray crystallography, Inorganic Chemistry, Physical Chemistry, Organic Chemistry, Tricarbonylrhenium (I) complexes, Dimethylamine, Tetramethyldiaminomethane
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).
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