Synthesis, Structural Characterisation and Electrochemical Studies of Neutral Alkenylcarbyne Tungsten Complexes Bearing Chelating Bidentate and Tridentate Phosphanes
✍ Scribed by Lei Zhang; M. Pilar Gamasa; José Gimeno; M. Fátima C. Guedes da Silva; Armando J. L. Pombeiro; Claudia Graiff; Maurizio Lanfranchi; Antonio Tiripicchio
- Publisher
- John Wiley and Sons
- Year
- 2000
- Tongue
- English
- Weight
- 400 KB
- Volume
- 2000
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
Neutral alkenylcarbyne complexes [X = SCN; n = 1 (2a), 4 (2b). X = OCN; n = 1 (2c), 4 (2d)] were prepared by reaction of the acetonitrile complexes [n = 1 (1a), 4 (1b)] with M[OCN] or M[SCN] (M = Na, K, Bu 4 N), and were fully characterised. The synthesis of complex 3, containing the tridentate phosphane triphos [triphos = PPh(CH 2 CH 2 PPh 2 ) 2 ], is also described. The structures of 2b and 3 were determined by Xray diffraction methods. In both complexes, the coordination of the W atom was octahedral, with the N-bonded thiocyanate (2b) or the chlorine (3) anions trans to the alkenylcarbyne group. The W-N and W-Cl bond lengths were significant longer than the average found in the literature; this indicates the remarkable trans influence of the alkenylcarbyne moiety. The electrochemical behaviour of complexes 2a-d and 3, as well as that of the related compounds D (2e: X = F, n = 4), (2f: X = Cl, n = 1), (2g: X = S 2 P(OEt) 2 , n = 1) and A (4: n = 1) was investigated by cyclic voltammetry (CV) and controlled [a