Ruthenium complexes bridges

Of particular interest are the cases where, by a suitable design of the complex, the factors (a) to (d) above can be eliminated so that the departure of the electrochemical response from the purely statistical behaviour arises solely from cause (e). Two examples of such complexes which have been well studied are binuclear ruthenium complexes bridged by 4,4 -bipyridyl type ligands, and binuclear complexes where L, the binucleating macrocyclic ligand, is a symmetric... 

The reaction of the coordinatively unsaturated ruthenium amidinates with [Cp RuCl]4 tetramer or [CpRufMeCNlsJPFg provides access to novel amidinate-bridged dinuclear ruthenium complexes (Scheme 146), which in turn can be transformed into cationic complexes or hydride derivatives. In these complexes, a bridging amidinate ligand perpendicular to the metal-metal axis effectively stabilizes the highly reactive cationic diruthenium species. 

Another method for reductive dimerization has been developed in hy-drosilylation. NiCl2-SEt2 is an effective catalyst in silylative dimerization of aromatic aldehydes with a hydrosilane (Scheme 12) [40]. A catalytic thiolate-bridged diruthenium complex [Cp RuCl(/ 2-SPrI)2RuCp ][OTf] also induces the conversion to 1,2-diaryl-1,2-disiloxyethane [41]. A dinuclear (siloxyben-zyl)ruthenium complex is considered to be formed, and the homolytic Ru - C bond fission leads to the siloxybenzyl radicals, which couple to the coupling product 14. 

Other mixed-valence metal complexes have been published that display electrochromic behavior, among them bipyridyl ruthenium complexes linked through dioxolene containing bridging ligands, such as 3,3, 4,4 -tetrahydroxybi-phenyl, 3,3",4,4"-tetrahydroxy-p-terphenyl, and 9-phenyl-2,3,7-trihydoxy-6-flu-orone [115,116] (Chart 3). Many of the redox processes that lead to frequently... 

Similar reactions are found with the iron and ruthenium complexes in which the metal-metal bonds are also bridged by //-CO or //-CMe2 groups (65, 66, 68) ... 

Similarly, treatment of the nickel-ruthenium complex 62 with a variety of donors (CO, CNCy, NCfBu, PPh3) affords the doubly bridged complexes 78-81 (Scheme 7), wherein the donor binds to ruthenium. However, upon treatment with PhC=CH, only one carbonyl adopts a bridging mode, the second bridge being provided by a r2 vinylidene (63), derived from a 1,2-hydride shift within the PhC=CH ligand. 

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