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Synthetic, structural, and spectroscopic studies of mixed sandwich Ru(II) complexes involving η6-p-cymene with monodentate fluorine-containing phosphines or phosphites

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Syntheses, structures, spectroscopy, and calculated structures for several Ru(II) complexes involving p-cymene and either fluorine-containing phosphines or phosphites are reported. The complexes are readily prepared by ligand substitution reactions from [{Ru(p-cymene)Cl2}2] to produce [Ru(p-cymene)(L)Cl2] {L = P(C6H4-p-F)3 (1), P(C6H4-p-CF3)3 (2), P(C6H3(m-CF3)2)3 (3), PPh3 (4), P(OCH2CF3)3 (5), P(OCH(CF3)2)3 (6), and POMe3 (7)}. The structures for all seven complexes are supported by UV–vis and multi-nuclear NMR spectroscopy. Five complexes are characterized by single-crystal X-ray crystallography (1, 3, 57) and exhibit a distorted octahedral structure involving three donors from one phosphine or phosphite ligand, two chlorides, and the facially coordinating η6-p-cymene ligand. Electronic structure theory computations have been performed on 17 along with the theoretical [Ru(p-cymene){P(C6F5)3}Cl2] (8). For all complexes, the HOMO is primarily Ru (d xy or ) in character. The LUMO shifts from primarily Ru (d xz or d yz) to primarily phosphine ligand π* as the number of fluorines increases.
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Keywords: Ru complexes; crystal structures; fluorine; p-Cymene; phosphine ligands; phosphite ligands

Document Type: Research Article

Affiliations: Department of Chemistry, The University of Tennessee at Chattanooga, Chattanooga, TN, USA

Publication date: January 2, 2016

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