COORDINATION OF POLYTHIAETHER MACROCYCLES TO METAL CLUSTER COMPLEXES .2. COORDINATION OF POLYTHIAETHER MACROCYCLES TO HEXARUTHENIUM CARBIDO CARBONYL CLUSTERS

The synthesis and structural characterizations of RU(6)(mu(6)-C) cluster complexes containing the polythiaether macrocycle ligands 1,5,9-trithiacyclododecane (12S3), 1,5,9,13-tetrathiacyclohexadecane (16S4), and 1,4,7-trithiacyclononane (9S3) are reported. The reactions of Ru-6(CO)(17)(mu(6)-C), 1, with 12S3 and 16S4 in refluxing octane solvent have yielded the new cluster complexes RU(6)(CO)(13)(mu-eta(3)-12S3)(mu(6)-C), 2, in 78% yield, and RU(6)(CO)(15)(mu-eta(2)-16S4)(mu(6)-C), 3, in 58% yield, respectively. The reaction of 1 with 9S3 in refluxing hexane solvent has yielded the new cluster complex RU(6)(CO)(14)(eta(3)-9S3)(mu(6)-C), 4, in 93% yield. All three products were characterized by a combination of IR, H-1 NMR, and single crystal X-ray diffraction analyses. All three compounds contain octahedral Rue clusters with a carbido ligand in the center. In compound 2 the three sulfur atoms of the 12S3 ligand are coordinated to one ruthenium atom but one of the sulfur atoms simultaneously serves as a bridge to an adjacent ruthenium atom. In compound 3 only two of the four sulfur atoms of the 16S4 ligand are coordinated to the cluster and they are coordinated to two adjacent ruthenium atoms. In compound 4 the three sulfur atoms of the 9S3 ligand are coordinated to one ruthenium atom only. When heated to 105 degrees C for 18 h, compound 4 was converted to the new compound RU(6)(CO)(14)(mu(3)-eta(3)-SCH2CH2SCH2CH2S)(mu(5)-C), 5, in 68% yield. The evolution of ethylene was observed by H-1 NMR spectroscopy. Compound 5 was obtained in one step from the reaction of 1 with 9S3 in refluxing octane solvent in 36% yield. Compound 5 was characterized crystallographically and was shown to consist of a ''spiked'' square pyramidal cluster of six metal atoms with the carbido ligand in the center of the base of the square pyramid. The spike is bonded to one of the metal atoms in the base of the square pyramid. The 9S3 ligand was converted into a triply bridging 3-thiapentane-1,5-dithiolato ligand. All three sulfur atoms form bridges between the ruthenium spike and the Rug square pyramid. Crystal data: for 2 . C6H6, space group = P1, a = 16.755(2) Angstrom, b = 11.647(2) Angstrom, c = 11.355(2) Angstrom, alpha = 61.30(1)degrees, beta = 89.78(1)degrees, gamma = 101.76(2)degrees, Z = 2, 2648 reflections, R = 0.032; for 3: space group = Pnma, a = 23.373(3) Angstrom, b = 17.643(2) Angstrom, c = 9.453(2) Angstrom, Z = 4, 1854 reflections, R = 0.030; for 4 . C6H6, space group = P21/a, alpha = 13.366(2) Angstrom, b = 20.746(6) Angstrom, c = 13.059(3) Angstrom, beta = 90.75(1)degrees, Z = 4, 3345 reflections, R = 0.025; for 5 . CH2Cl2, space group = P2(1)/c, a = 13.669(2) Angstrom, b = 15.610(3) Angstrom, c = 15.476(2) Angstrom, beta = 92.46(1)degrees, Z = 4, 4526 reflections, R = 0.033.