Octahedral Alkynylphosphine Ruthenium(II) Complexes: Synthesis, Structure, and Electrochemistry

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• 作者：Jesu虂s Berenguer ; Mari虂a Bernechea ; Julio Ferna虂ndez ; Bele虂n Gil ; Elena Lalinde ; M. Teresa Moreno ; Santiago Ruiz ; Sergio Sa虂nchez
• 刊名：Organometallics
• 出版年：2011
• 出版时间：September 12, 2011
• 年：2011
• 卷：30
• 期：17
• 页码：4665-4677
• 全文大小：1190K
• 年卷期：v.30,no.17(September 12, 2011)
• ISSN：1520-6041

文摘

Reaction of [RuCl₂(PPh₃)₃] with excess of PPh₂C鈮Fc (Fc = ferrocenyl) proceeds with formation of [trans-RuCl₂(PPh₂C鈮Fc)₄] (3), which reacts with HC鈮R (R = Ph, Tol) via dissociative loss of one PPh₂C鈮Fc ligand to yield vinylidene complexes [mer,cis-RuCl₂(C鈺怌HR)(PPh₂C鈮Fc)₃] (R = Ph 4a, Tol 4b). Reported herein also is the preparation of a series of trans/cis bis(alkynyl)tetrakis(alkynylphosphine) derivatives [Ru(C鈮R鈥?₂(PPh₂C鈮R)₄] (R鈥?= Ph, Tol; R = Ph, trans/cis-5a, 5b; R = Tol, trans/cis-6a, 6b; R = Fc, trans/cis-7a, 7b), synthesized by reaction of [trans-RuCl₂(PPh₂C鈮R)₄] (R = Ph 1, Tol 2, Fc 3) with an excess of HC鈮R鈥?(R鈥?= Ph, Tol) and NEt₃, in the presence or absence of NaPF₆. In the preparation of cis-5a, the ketovinyl derivative [mer-Ru{魏C,O-C(CH₂COCH₃)鈺怌HPh}Cl(PPh₂C鈮Ph)₃] (8) was obtained as a byproduct in the presence of acetone. The solid-state structures of complexes 3, trans-5a, trans-7a, and 8 have been determined by X-ray diffraction studies, showing the presence of several types of weak intramolecular hydrogen interactions. The cyclic voltammetry data for the mononuclear complexes (1, 2, trans/cis-5/6, and 8) show a quasi reversible oxidation attributed to the Ru^II/III couple and reveal a marked influence of the ligands and the geometry on the E_1/2 values. The electrochemical behavior of the ferrocenylethynyldiphenylphosphine compounds 3, 4, and trans/cis-7 is more complex. Spectroelectrochemical comparative studies of related complexes (trans-7b vs trans-5b; 4 vs [RuCl₂(C鈺怌HTol)(PPh₂C鈮Ph)₃]) suggest that the first oxidation occurs at the ferrocene site of the PPh₂C鈮Fc ligand.