219815-97-1Relevant academic research and scientific papers
Ligand-assisted heterolytic activation of hydrogen and silanes mediated by nitrosyl rhenium complexes
Llamazares, Angela,Schmalle, Helmut W.,Berke, Heinz
, p. 5277 - 5288 (2008/10/08)
Abstraction of the hydride in the dinitrosyl rhenium complexes [Re(H)(NO)2(PR3)2] (R = iPr (1a), Cy (1b)) affords the dinuclear saturated compounds [Re2(H)(μ,η2-NO)(NO)3(PR3) 4][BAr4′] (R = iPr, 2a; Cy, 2b) or the mononuclear unsaturated 16-electron derivatives [Re(NO)2(PR3)2][BAr4′] (R = iPr, 3a; Cy, 3b). In complexes 2a,b the metal centers are connected via a nitrosyl-isonitrosyl linkage. Complexes 2 and 3 react with classical two-electron donor ligands such as CH3CN, CO, C6H5CHO, and THF, but also with H2 and HSiEt3. In the two latter cases heterolytic rupture of the hydrogen-hydrogen or hydrogen-silicon bonds is achieved. Complexes 2a,b and 3a,b are active in the catalytic scrambling of H2/D2 to give HD under very mild conditions. In the presence of tetramethylpiperidine as a base the reaction of these complexes with H2 produces [Re(H)(NO){NOH2NC5H6(CH3) 4}(PR3)2][BAr4′] (R = iPr, 9a; Cy, 9b). Heterolysis of HSiEt3 mediated by 2a,b and 3a,b results in the formation of [Re(H)(NO)(NOSiEt3) (PR3)2][BAr4′] (R = iPr, 8a; Cy, 8b). Complexes 8a and 9b have been characterized by X-ray diffraction studies.
