Synthesis and reactivity of N,N,N′,N′-tetramethyldiaminomethane complexes of tricarbonylrhenium(I). X-ray molecular structures of [ReBr(CO)3(TMDM)] and [{Re(bipy)(CO)3}2(μ-OH)][SbF6]

Author(s): Peter J. Heard | Phunrawie Sroisuwan | and Derek A. Tocher.

Type of publication: Journal paper

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(μ-OH2)][SbF6]2 (2) and [Re(OH)(CO)3(bipy)] (3). 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(μ-OH2)][SbF6]2 (2) and [Re(OH)(CO)3(bipy)] (3).

Date Published: March 27 2003

Publication title: Polyhedron

Publisher: Elsevier

Place of publication: London United Kingdom

Pages: 1321-1327

Subject(s): Chemistry

DOI: https://doi.org/10.1016/S0277-5387(03)00102-5

Keywords: Tricarbonylrhenium (I) complexesTetramethyldiaminomethaneDimethylamineX-ray crystallography

Depositing User: Luke Miller