Reactions of ether-phosphine ruthenium hydride complexes with carbon disulfide and phenylacetylene: Crystal structures of RuCl(P ～ O) 3(η2-S2CH) and Ru(CO) Cl(P ～ O) 2(η2-S2CH)

Article abstract of DOI:10.1016/0022-328X(95)05950-T

The dithioformato complexes RuCl(P ～ O) ₃(η²-S₂CH) (2a,b) and RuCl(P ∩ O)(P ～ O)(η²-S₂CH) (3a,b) are accessible by insertion of CS₂ into the Ru-H bond of the (ether-phosphine)(hydrido)ruthenium complexes RuClH(P ∩ O)(P ～ O)₂ (1a,b) [P ～ O = η¹(P)-coordinated, P ∩ O = η₂(O,P)-chelated; O,P = diphenyl(2-methoxyethyl)phosphine (a), ( 1,3-dioxan-2-ylmethyl) diphenylphosphine (b)]. Treatment of 2a, 3a and 2b, 3b with carbon monoxide in CH₂Cl₂ results in the formation of the carbonyl complexes Ru(CO)Cl(P ～ O)₂(η²-S₂CH) (4a,b). The structures of 2a and 4a were determined by single crystal X-ray diffraction analyses. Crystal data for 2a: space group Pca2₁ , with a = 17.578(4) A, b = 14.215(3) A, c = 17.934(4) A, V = 4481(2) A³, Z = 4. The structure was refined to R = 0.037, wR = 0.082. Crystal data for 4a: space group P2₁/n with a = 12.009(2) A, b - 17.143(4) A, c = 16.510(4) A, β = 107.92(2)°, V-3234(1) A₃, 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)₂(C≡CPh) (5a,b) with evolution of dihydrogen. Carbonylation of 5a yields the cis-η¹(P)-coordinated complex RuCl(CO)₂(P ～ O)₂(C≡CPh) (6). If chloride is abstracted from Ru(CO)Cl(P ～ O)₂(η²-S₂CH) (4a) with AgBF₄ in THF the P ∩ O-chelated complex [Ru(CO)(P ∩ O)(P ～ O)(η²-S₂CH)][BF₄] (7) is obtained. Upon reaction of 7 with PhC≡CH the Ru-O bond is cleaved and instead of an η¹-vinylidene species the acetylide complex Ru(CO)(P ～ O)₂(η²-S₂CH)C≡CPh) (8) is formed.