Abstract
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, 5–7) 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 1–7 along with the theoretical [Ru(p-cymene){P(C6F5)3}Cl2] (8). For all complexes, the HOMO is primarily Ru (dxy or ) in character. The LUMO shifts from primarily Ru (dxz or dyz) to primarily phosphine ligand π* as the number of fluorines increases.
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Acknowledgments
The single-crystal X-ray diffraction structures were solved and refined at the 2013 American Crystallographic Association Single-Crystal X-Ray Crystallography Course at Northwestern University. Also, Patrick Zdunek (UTC) is thanked for his work obtaining the variable temperature 1H NMR spectra.
Disclosure statement
No potential of conflict of interest was reported by the authors.