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Coordinating Tectons: Bimetallic Complexes from Bipyridyl Terminated Group 8 Alkynyl Complexes

DOI: 10.1021/om500172r DOI Help

Authors: George A Koutsantonis (University of Western Australia) , Paul J Low (University of Western Australia) , Campbell F R Mackenzie (University of Western Australia) , Brian W Skelton (University of Western Australia) , Dmitry S Yufit (Durham University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Organometallics , VOL 33 (18) , PAGES 4911-4922

State: Published (Approved)
Published: August 2014
Diamond Proposal Number(s): 6749

Abstract: Bipyridyl appended ruthenium alkynyl complexes have been used to prepare a range of binuclear homometallic ruthenium and heterometallic ruthenium–rhenium complexes. The two metal centers are only weakly coupled, as evinced by IR and UV–vis–near NIR spectroelectrochemical experiments and supported by quantum chemical calculations. The alkynyl complexes of the type [Ru(C≡Cbpy){Ln}] ({Ln} = {(PPh3)2Cp}, {(dppe)Cp*}, {Cl(dppm)2}) undergo reversible one-electron oxidations centered largely on the alkynyl ligands, as has been observed previously for closely related complexes. The homometallic binuclear complexes, exemplified by [Ru(C2bpy-κ2-N′N-RuClCp)(PPh3)2Cp] undergo two essentially reversible oxidations, the first centered on the (C2bpy-κ2-N′N-RuClCp) moiety and the second on the Ru(C≡Cbpy)(PPh3)2Cp fragment, leading to radical cations that can be described as Class II mixed-valence complexes. The heterometallic binuclear complexes [Ru(C2bpy-κ2-N′N-ReCl(CO)3){Ln}] display similar behavior, with initial oxidation on the ruthenium fragment giving rise to a new optical absorption band with Re → Ru(C≡Cbpy) charge transfer character. The heterometallic complexes also exhibit irreversible reductions associated with the Re hetereocycle moiety.

Subject Areas: Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction