부산대학교 도서관

Syntheses, structures, spectroscopy, and calculated structures for several Ru(II) complexes involvingp-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 on1–7along with the theoretical [Ru(p-cymene){P(C6F5)3}Cl2] (8). For all complexes, the HOMO is primarily Ru (dxyor) in character. The LUMO shifts from primarily Ru (dxzordyz) to primarily phosphine ligandπ* as the number of fluorines increases. [ABSTRACT FROM PUBLISHER]