Reactions of ether-phosphine ruthenium hydride complexes with carbon disulfide and phenylacetylene: crystal structures of Ru(CO) Cl(P ∼ O) 3( η2-S 2CH and Ru(CO) Cl(P ∼ O) 2( η2-S 2CH)

Abstract

The dithioformato complexes RuCl(P ∼ O) 3( η 2CH) ( 2ab) and RuCl( P ⋒ O( P ∼ O)(η 2- S 2 CH ) ( 3ab) are accessible by insertion of CS 2 into the RuH bond of the (ether-phosphine)(hydrido)ruthenium complexes RuCl( P ⋒ O)( P ∼ O) 2 ( 1a,b) [P ∼ O = η 1(P)-coordinated, P ⋒ O = η 2 ( O,P )-chelated; O,P = diphenyl(2-methoxyethyl)phosphone ( a), (1,3-dioxan-2-methyl) diphenylphosphine ( b)]. Treatment of 2a, 3a and 2b, 3b with carbon monoxide in CH 2Cl 2 results in the formation of the carbonyl complexes Ru(CO)Cl(P ∼ O) 2( η 2S 2CH) ( 4a,b). The structures of 2a and 4a were determined by single crystal X-ray diffraction analyses. Crystal data for 2a: space group Pca2 1 with a = 17.578(4) A ̊ , b = 14.215(3) A ̊ , c = 17.934(4) A ̊ , V = 4481(2) A ̊ 3, Z = 4 . The structure was refined to R = 0.037, wR = 0.082. Crystal data for 4a: space group P 1/ n with a = 12.009(2) A ̊ , b = 17.143(4) A ̊ , c = 16.510(4) A ̊ , β = 107.92(2)°, V = 3234(1) A ̊ 3, Z = 4 . The structure was refined to R = 0.035, wR = 0.087. 1a,b react with phenylacetylene to give the acetylide complexes RuCl( P ⋒ O( P ∼ O) 2( CCPh ) 5a,b with evulition of dihydrogen. Carbonylation of 5a yields the cis- η 1(P-coordinated complex RuCl( P ⋒ O( P ∼ O) 2( CCPh ) ( 6). If chloride is abstracted from Ru(CO) Cl(P ∼ O) 2( η 2-S 2CH) ( 4a) with AgBF 4 in THF the P ⋒ O-chelated complex Ru(CO) Cl(P ∼ O) 2( η 2-S 2CH][BF 4] ( 4) is obtained. Upon reaction of 7 with PhCCH the RuO bond is cleaved and instead of an η 1-vinylidene species the acetylide complex Ru(CO) Cl(P ∼ O) 2( η 2-S 2CH) ( 8) is formed.