Structural consequences of electron-transfer reactions 17. Electrochemically induced reversible insertion of ruthenium atoms into an eight-carbon chain

Selective cleavage of unactivated arene ring C–C bonds by iridium: key roles of benzylic C–H activation and metal–metal cooperativity

“…5 and S11) is too stable to react further. In contrast, the formation of metal-metal bond is usually thought to facilitate rather than interfere with the desired metal-assisted chemistries, including in non-selective C-C cleavage in arenes, 11,12,16,18 and other aromatic and unsaturated hydrocarbons (biphenylene, 27 cyclooctatetraene, 28,29,57,58 and cyclopentadienyl 18 anions, cycloalkenes 30 and alkynes [31][32][33] ). These roles of the anti-Ir 2 intermediate in determining the outcome of thermolysis of Cp*Ir(arene) complexes appears to be general, as suggested by our calculations on benzene and mxylene analogues of 1 (Table S12).…”

Triple-decker transition metal complexes bridged by a single carbocyclic ring

“…The tub form of the bridging ligand undergoes substantial flattening, taking on the ''twist'' form characteristic of the l-g 5 :g 5 complexes and finally (reversibly) breaking a C-C bond to give the 10-membered metallacycles found in the flyover complexes depicted in Fig. 25 [125].…”

Binuclear Complexes of Ruthenium and Osmium Containing Metal Metal Bonds

“…Oxidation of [Ru 2 (r| ,r| -C 5 H 4 CH 2 C 5 H 4 ) 2 ] by benzoquinone/BF 3 Et 2 O similarly gives rise to a dicationic product [Ru 2 (rj ,r| -C 5 H 4 CH 2 C 5 H 4 ) 2 ] in which the two ruthenium atoms are linked directly by a ruthenium-ruthenium bond. 427 Furthermore, the pseudo triple-decker complex [Ru 2 Cp 2 (cot)] 428 is also readily and reversibly oxidized to a dicationic species, [Ru 2 Cp 2 (cot)] 2+ (246)*, 429 ' 430 with this oxidation process being accompanied by an opening of the eight-carbon chain and the concomitant formation of a ruthenium-ruthenium bond. 429 …”

“…427 Furthermore, the pseudo triple-decker complex [Ru 2 Cp 2 (cot)] 428 is also readily and reversibly oxidized to a dicationic species, [Ru 2 Cp 2 (cot)] 2+ (246)*, 429 ' 430 with this oxidation process being accompanied by an opening of the eight-carbon chain and the concomitant formation of a ruthenium-ruthenium bond. 429 …”