Mixed heterotri- to heteropentametallic transition-metal complexes: Synthesis, characterization and electrochemical behavior

作者：Packheiser Rico; Ecorchard Petra; Rueffer Tobias; Walforta Bernhard; Lang Heinrich^*

来源：European Journal of Inorganic Chemistry, 2008, (26): 4152-4165.

DOI：10.1002/ejic.200800457

• heteromultimetallic complexes
• transition metals
• acetylides
• cyclic voltammetry

The synthesis and reaction chemistry of heteromultimetallic transition-metal complexes are discussed. Complex [(eta(2)-dppt)(eta(5)-C5H5)Ru-C C-C6H4-4-PPh2] (3) [dppt = 1,1'-bis(diphenylphosphanyl)ferrocene], accessible by treating [eta(2)-doppf)(eta(5)-C5H5)RuCl] (1) with equimolar amounts of HC C-C6H4-4-PPh2 (2), gives on treatment with [(cod)RhCl](2) (4), [(eta(2)-dppf)(eta(5)-C5H5)Ru-C C-C(6)G(4)-4-PPh2-(Rh)] [5, {Rh} = (cod)RhCl; 7, {Rh} = (eta(5)-C5Me5)RhCl2] and [eta(2)-dppf)(eta(5)-C5H5)Ru-C C-C6H4-4-PPh2-AuCl] (9), respectively. Tetra- and even pentametallic heteronuclear complexes can be prepared by following consecutive reaction sequences: Treatment of 9 with HC CR {10a, R = C5H4N-4; 10b, R = C6H4-4-C N; 10c, R = bpy (= 2,2'-bipyridyl-5-yl); 12a, R = bpy[-Re(CO)(3)Cl]} in the presence of HNEt2 and [CuI] gave [(eta(2)-dppf)(eta(5)-C5H5)Ru-C C-C6H4-4-PPh2-Au-C CR] {11a, R = C5H4N-4; 11b, R = C6H4-4-C N; 11c, R = bby; 13, R = bpy-(Re(CO)(3)Cl]}. Compound 11c is the key starting material for complexes of higher nuclearity. Treatment of 11c with [(nbd)-Mo(CO)(4)] (14) afforded heterotetrametallic {eta(2)-dppf)(eta(5)-C5H5)Ru-C C-C6H4-4-PPh2-Au-C C-bpy[Mo(CO)(4)]} (15), whereas with [{[Ti](mu-sigma,pi-C CSiMe3)(2)}M]X [16a, MX = Cu(N CMe)PF6; 16b, MX = AgOClO3] novel heteropentametallic [eta(2)-dppf)(eta(5)-C5H5)Ru-C C-C6H4-4-PPh2-Au-C C-bpy({[Ti](mu-sigma,pi-C CSiMe3)(2)}M)]X (17a, M = Cu, X = PF6; 17b, M = Ag, X = ClO4) is formed. The reaction of 11a with [{[Ti](mu-sigma,pi-C CSiMe3)(2)]Cu]OTf (16c) produced [eta(2)-dppf)-(eta(5)-C5H5)Ru-C C-C6H4-4-PPh2-Au-C C-4-C5H4N({[Ti](mu-sigma,pi-C CSiMe3)(2)}Cu)]OTf (18). The structure of 9, 11b, 11c, and 12 in the solid state and the electrochemical behavior of selected complexes are also reported.

• 出版日期2008-9