Vinyl Ruthenium-Modified Biphenyl and 2,2′-Bipyridines

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SCHEERER, Stefan, Nils ROTTHOWE, Obadah S. ABDEL-RAHMAN, Xiaoyan HE, Stéphane RIGAUT, Hana KVAPILOVÁ, Stanislav ZÁLIŠ, Rainer F. WINTER, 2015. Vinyl Ruthenium-Modified Biphenyl and 2,2′-Bipyridines. In: Inorganic Chemistry. 54(7), pp. 3387-3402. ISSN 0020-1669. eISSN 1520-510X

@article{Scheerer2015Vinyl-31108, title={Vinyl Ruthenium-Modified Biphenyl and 2,2′-Bipyridines}, year={2015}, doi={10.1021/ic503075e}, number={7}, volume={54}, issn={0020-1669}, journal={Inorganic Chemistry}, pages={3387--3402}, author={Scheerer, Stefan and Rotthowe, Nils and Abdel-Rahman, Obadah S. and He, Xiaoyan and Rigaut, Stéphane and Kvapilová, Hana and Záliš, Stanislav and Winter, Rainer F.} }

We report here on ruthenium alkenyl complexes 2 and 3 derived from 2,2′-bipyridine and their Re(CO)<sub>3</sub>X adducts 4a,b and 5. Detailed electrochemical studies on these complexes and spectroscopic characterization of their oxidized forms by IR, UV/vis/NIR, and electron paramagnetic resonance spectroscopies as well as quantum chemical studies reveal sizable (bridging) ligand contributions to the redox orbitals. Engagement of the free bipy functions of complexes 2 and 3 in binding to the electron-withdrawing fac-Re(CO)<sub>3</sub>X (X = Br, Cl) moiety enhances the metal-to-ligand charge-transfer character of the optical excitations, causes sizable anodic shifts of the redox potentials, and decreases the number of observable anodic redox waves by one when compared to complexes 2 and 3. Despite the decreasing electron density at the terminal or bridging alkenyl bipyridine ligand, the anodic redox processes still maintain appreciable ligand character as is seen by the shifts of the Ru(CO) and Re(CO)<sub>3</sub> stretching frequencies on oxidation. Binding of the fac-Re(CO)<sub>3</sub>X moiety also attenuates the degree of ground-state delocalization in the mixed-valent states. Rigaut, Stéphane eng Kvapilová, Hana Abdel-Rahman, Obadah S. 2015-06-03T08:37:54Z Rigaut, Stéphane Rotthowe, Nils Rotthowe, Nils Scheerer, Stefan 2015-06-03T08:37:54Z Záliš, Stanislav He, Xiaoyan 2015 Scheerer, Stefan Winter, Rainer F. Winter, Rainer F. Záliš, Stanislav Kvapilová, Hana He, Xiaoyan Abdel-Rahman, Obadah S. Vinyl Ruthenium-Modified Biphenyl and 2,2′-Bipyridines

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