REACTIONS OF ETHER-PHOSPHINE RUTHENIUM HYDRIDE COMPLEXES WITH CARBON-DISULFIDE AND PHENYLACETYLENE - CRYSTAL-STRUCTURES OF RUCL(P-SIMILAR-TO-O)(3)(ETA(2)-S2CH) AND RU(CO)CL(P-SIMILAR-TO-O)(2)(ETA(2)-S2CH)

The dithioformato complexes RuCl(P similar to O)(3)(eta(2)-S2CH) (2a,b ) and RuCl(P boolean AND O)(P similar to O)(eta(2)-S2CH) (3a,b) are ac cessible by insertion of CS2 into the Ru-H bond of the (ether-phosphin e)(hydrido)ruthenium complexes RuClH(P boolean AND O)(P similar to O)( 2) (1a,b) [P similar to O = eta(1)(P)-coordinated, P boolean AND O = e ta(2)(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 ca rbonyl complexes Ru(CO)Cl(P similar to O)(2)(eta(2)-S2CH) (4a,b). The structures of 2a and 4a were determined by single crystal X-ray diffra ction analyses. Crystal data for 2a: space group Pca2(1) with a = 17.5 78(4) Angstrom, b = 14.215(3) Angstrom, c = 17.934(4) Angstrom, V = 44 81(2) Angstrom(3), Z = 4. The structure was refined to R = 0.037, wR = 0.082. Crystal data for 4a: space group P2(1)/n with a = 12.009(2) An gstrom, b = 17.143(4) Angstrom, c = 16.510(4) Angstrom, beta = 107.92( 2)degrees, V = 3234(1) Angstrom(3), Z = 4. The structure was refined t o R = 0.035, wR = 0.087. 1a,b react with phenylacetylene to give the a cetylide complexes RuCl(P boolean AND O)(2)(C=CPh) (5a,b) with evoluti on of dihydrogen. Carbonylation of 5a yields the cis-eta(1)(P)-coordin ated complex RuCl(CO)(2)(P similar to O)(2)(C=CPh) (6). If chloride is abstracted from Ru(CO)Cl(P similar to O)(2)(eta(2)-S2CH) (4a) with Ag BF4 in THF the P boolean AND O-chelated complex [Ru(CO)(P boolean AND O)(P similar to O)(eta(2)-S2CH)][BF4] (7) is obtained. Upon reaction o f 7 with PhC=CH the Ru-O bond is cleaved and instead of an eta(1)-viny lidene species the acetylide complex Ru(CO)(P similar to O)(2)(eta(2)- S2CH)(C=CPh) (8) is formed.