86776-92-3Relevant articles and documents
The chemistry of new nitrosyltungsten complexes with pyridyl- functionalized phosphane ligands
Baur, Juergen,Jacobsen, Heiko,Burger, Peter,Artus, Georg,Berke, Heinz,Dahlenburg, Lutz
, p. 1411 - 1422 (2007/10/03)
The coordination chemistry of pyridylphosphanes, such as 2(6-tert- butylpyridyl)diphenylphosphane (Ph2P-tert-Bupy) (6) and 2-(6-tert- butylpyridyl)dimethylphosphane (Me2P-tert-Bupy) (7) towards a number of nitrosyltungsten complexes is reported. Displacement of the loosely coordinated MeCN from [W(CH3CN)3(CO)2(NO)][BF4] led to the following cationic compounds incorporating mono- and bidentate coordinated phosphane ligands: cis,cis-[W(CO)2(NO)(Ph2PR)(η2-Ph2PR)][BF4], [R = 2-pyridyl (9a), 2-picolyl (11)], cis,cis-[W(CO)(NO)(η2-Ph2Ppy)2][BF4] (20), trans,trans-[W(CO)(NO)(η2-Ph2Ppy)2][BPh4] (21), fac-[W(CO)2(NO) (Me2P- py)3][BF4] (16), fac-[W(CO)2(NO)(Me2P-tert-Bupy)3][BF4] (18), cis,cis- [W(CO)2(NO)(Me2Ppy)(η2-Me2Ppy)][BF4] (22), and cis,cis- [W(CO)2(CH3CN)(NO)(Me2P-tert-Bupy)2][BF4] (23a). The cationic complex cis,mer-[W(CO)3(NO)(Ph2P-tert-Bupy)2][PF6] (14) has been prepared by nitrosylation of cis/trans-W(CO)4(Ph2P-tert-Bupy)2 (13). Reactions of 9a, 11, 14, 16, and 18 with hydride transfer reagents afforded trans,- trans- HW(CO)2(NO)(Ph2Ppy)2 (10), trans, trans-HW(CO)2(NO)(Ph2Ppic)2 (12), trans, trans-HW(CO)2(NO)(Ph2-tBupy)2 (15), cis/trans- HW(CO)2(NO)(Me2Ppy)2 (17), and cis/trans-HW(CO)2(NO)(Me2P-tert-Bupy)2 (19), respectively. Reactivity experiments with acetic acid, hydroiodic acid, carbon dioxide, and acetylenedicarboxylic acid were performed, and were found to afford trans-W(CO)(NO)(Ph2Ppy)2(η2-CH3CO2) (24), trans, trans- IW(CO)2(NO)(Ph2Ppy)2 (25), trans-W(HCO2)(CO)2(NO)(Ph2Ppy)2 (26), and trans-W{η2-(Z)C(CO2Me)=CH[C(O)OMe]}(CO)(NO)(Ph2Ppic)2 (27), respectively. The influence of the pyridyl substituent in 10 was probed by a comparative H/D exchange experiment in which 10 and the analogous complex HW(CO)2(NO)(PPh3)2 were treated with MeOD. The deuterated complex trans,trans-WD(CO)2(NO)(Ph2Ppy)2 (28) could be isolated. The structures of 9a, 11, 14, and 20 have been determined by single-crystal X-ray diffraction analysis.
