SYNTHESES AND X-RAY STUDIES OF RUTHENIUM CLUSTERS OBTAINED BY REACTION OF (ALKYLTHIO)ALKYNES RC-CSC2H5 (R=CH3, C6H5) WITH [RU-3(CO)(12)]

By reaction of [RU(3)(CO)(12)] With RC=CSC2H5 (R = CH3, C6H5), six typ es of compounds were obtained: (a) [Ru-3(CO)(9)(mu(2)-SC2H5) (mu(3)-C= CR)] compounds I (R = CH3, 30% yield) and II(R C6H5, 46% yield) were s ynthesized. Both structures are built on an open Ru-3 triangle and con tain two ligands, SC2H5 and C=CR, resulting from the cleavage of RC=C- SC2H5. Crystals of I are triclinic, space group P ($) over bar 1, with a = 9.284(3) Angstrom, b = 9.319(4) Angstrom, c = 14.036(3) Angstrom, alpha = 83.67(3)degrees, beta = 72.71(5)degrees, gamma = 62.28(4)degr ees, and Z = 2. Crystals of II are monoclinic, space group Cc,;with a = 15.951(9) Angstrom, b = 12.520(4) Angstrom, c = 12.881(4) Angstrom b eta = 113.20(2)degrees, and Z = 4. (b) [Ru-4(CO)(12)(mu(2)-SC2H5)(mu(4 )-C=CR)] compounds III (R = CH3) and IV (R = C6H5 4% yield) were synth esized. Both structures are based on a Ru-4 Square plane containing fr agments of the thioalkyne. The mu(4)-acetylide fragment spans one side of the square plane while the ethylthio group bridges one edge. Cryst als of III are monoclinic, space group P2(1)/n, with a = 9,440(3) Angs trom, b = 15.822(1) Angstrom, c = 16.491(2) Angstrom, beta = 94.24(2)d egrees, and Z = 4. Crystals of IV are triclinic, space group P1, a = 1 7.282(6) Angstrom; b = 9.587(6) Angstrom, c = 9.674(4) Angstrom, alpha = 61.38(5)degrees, beta = 100.36(3)degrees, gamma = 94.63(5)degrees, and Z = 2. (c) C2H5)(mu(3)SC(2)H(5))(mu(2)-C=CCH3)(mu(4)-C=CCH3)] comp ound V (13% yield) was made. This structure is based on a Ru-4 Square plane sharing an edge with a Ru-3 triangle containing fragments of two thioalkyne molecules One ethylthio fragment bridges a Ru-Ru bond whil e the second bridges three ruthenium atoms.;;One acetylide fragment sp ans one side of the square plane as for III and IV, while the second i s sigma,pi-ligated. Crystals of V are triclinic, space group P ($) ove r bar 1, with a = 10.014(1) Angstrom, b = 10.464(2) Angstrom, c = 16.1 79(3) Angstrom, alpha = 91.50(3)degrees, beta = 101.52(2)degrees, gamm a = 111.37(1)degrees, and Z = 2. (d) (7){mu(3)-S(C2H5)CC(C6H5)C(SC2H5) C(C6H5)CC(C6H5)}- (mu(2)-SC2H5)] compound VI (3% yield) was synthesize d. The structure contains a Ru-3 chain and a pentasubstituted cyclopen tadienyl mu(3)-ligand which resulted from the coupling of two ligand m olecules and one acetylide fragment. Crystals of VI are monoclinic, sp ace group P2(1)/n, with a 20.447(6) Angstrom, b = 17.924(8) Angstrom, c = 10.619(3) Angstrom, beta = 100.86(4)degrees, and Z = 4. (e) (CO)(1 3)(mu(2)SC(2)H(5))2{mu(5)-C(C6H5)CC(C6H5)C}] compound VII (4.5% yield) was synthesized. The unsymmetrical structure is based on a ruthenium triangle and two Ru(CO)3 groups attached with bridging fragments of tw o thioalkyne molecules. Each ethylthio fragment bridges two ruthenium atoms. Both acetylide fragments are coupled in head to tail manner to yield-the sigma,pi-mu(5)-C(C6H5)CC(C6H5)C ligand. Crystals of VII are triclinic, space group P ($) over bar 1, with a = 9.279(3) Angstrom, b = 12.318(8) Angstrom, c = 17.921(11) Angstrom, alpha = 84.31(4)degree s, beta = 83.15(4)degrees, gamma = 69.43(4)degrees, and Z = 2. (f) (6) (CO)(14)(mu(2)-SC2H5)(2){mu(6)-C(CH3)CCC(CH3)}] compound VIII (2% yiel d) was synthesized. The structure is based on a rhombic six-atom-raft geometry containing fragments of two thioalkyne molecules. Each ethylt hio group bridges one Ru-Ru bond. The acetylide fragments are coupled tail to tail, forming a C(CH3)CCC(CH3) sigma pi-mu(6)-ligand. Crystals of VIII are monoclinic, space group P2(1)/n, with a = 20.815(3) Angst rom, b = 19.254(8) Angstrom, c = 8.692(8) Angstrom, beta = 92.49(2)deg rees, and Z = 4.