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Bimetallic reaetivity. Oxidative-addition and reductive-elimination reactions of rhodium and iridium bimetallic complexes
Schenck, Terry G.,Milne,Sawyer,Bosnich
, p. 2338 - 2344 (2008/10/08)
Homobimetallic complexes of rhodium(I) and iridium(I) containing the binucleating ligand PNNP undergo oxidative-addition and reductive-elimination reactions with acetyl chloride and methyl iodide. Depending on the electron richness of the metals, a complete spectrum of possibilities is observed from reversible single oxidative addition on one of the metals to irreversible double oxidative addition on both metals. Oxidative addition to one metal leads to deactivation of the other metal despite the fact that no metal-metal bonds are formed. A crystal structure of a rhodium(I)-rhodium(III) complex [Rh2(μ-PPh2)(CO)2PNNP-(CH 3)I]·C4H10O has been determined and shows the two metals to be separated by 3.766 A?. Crystals are triclinic, space group P1, a = 12.211 (4) A?, b = 13.313 (7) A?, c = 15.616 (7) A?, a = 79.34 (5)°, α = 72.64 (3)°, γ = 84.37 (4)°, V = 2379 A?3, Dcalcd = 1.57 g cm-3 for Z = 2, and R = 0.0401 for 6739 observed (I > 3σ(I)) reflections. The bis(diene) species of rhodium and iridium are precursors for catalytic hydrogenation of alkenes and alkynes.
