caa a22 4500 477085342 CHVBK 20180405111502.0 cr unu---uuuuu 170330e19960301xx s 000 0 eng 10.1007/BF01166176 doi (NATIONALLICENCE)springer-10.1007/BF01166176 Triosmium clusters derived from the reactions of thioureas with dodecacarbonyltriosmium: Crystal structures of [Os3(CO)11{ η 1-SC(NMe2)2}], [Os3(CO)9( μ -OH)( μ -OMeOCO){ η 1-SC(NMe2)2}] and [( μ -H)Os3(CO)9{ μ 3-NHC(S)NH2}] [Elektronische Daten] [Kazi Azam, Rahima Dilshad, Shariff Kabir, Rashid Miah, Mohammad Shahiduzzaman, Edward Rosenberg, Kenneth Hardcastle, Michael Hursthouse, K. Abdul Malik] The reaction of [Os3(CO)12] with tetramethylthiourea in the presence of a methanolic solution of Me3NO·2H2O at 60° yields the compounds [Os3(CO)11{η 1-SC(NMe2)2}] (1) in 56% yield and [Os3(CO)9(μ-OH)(μ-MeOCO){η 1-SC(NMe2)2}] (2) in 10% yield in which the tetramethylthiourea ligand is coordinatedvia the sulfur atom at an equatorial position. Compound2 is a 50 e− cluster with two metal-metal bonds and the hydroxy and methoxycarbonyl ligands bridging the open metal-metal edge. In contrast, the analogous reaction of [Os3(CO)12] with thiourea gives the compounts [(μ-H)Os3(CO)10{μ-NHC(S)NH2}] (3) in 8% yield and [(μ-H)Os3(CO)9{3-NHC(S)NH2}] (4) in 30% yield. In3, the thioureato ligand bridges two osmium atomsvia the sulfur atom, whereas in4 in addition to the sulfur bridge, one of the nitrogen atoms of thioureato moiety bonds to the remaining osmium atom. The decacarbonyl compounds 3 can also be obtained in 50% yield from the reaction of [Os3(CO)10(MeCN)2] with thiourea at ambient temperature. Compound3 converts to4 (65%) photochemically. Compound1 reacts with PPh3 and acetonitrile at ambient temperature to give the simple substitution products [Os3(CO)11(PPh3)] and [Os3(CO)11(MeCN)], respectively, while with pyridine, the oxidative addition product [(μ-H)Os3(CO)10(μ-NC5H4] is formed at 80°C. All the new compounds are characterized by IR,1-H-NMR and elemental analysis together with the X-ray crystal structures of1,2 and4. Compound1 crystallizes in the triclinic space group P $$P\bar 1$$ with unit cell parametersa = 8.626(3) Å,b = 11.639(3) Å,c = 12.568(3_ Å,α = 84.67(2)°,β = 75.36(2)°,γ = 79.49(3)°,V = 1199(1) Å3, andZ = 2. Least-squares refinement of 4585 reflections gave a final agreement factor ofR = 0.0766 (R w = 0.0823). Compound2 crystallizes in the monoclinic space group P21/n with unit cell parametersa = 9.149(5) Å,b = 17.483(5) Å,c = 15.094(4) Å,β = 91.75(2)°,V = 2413(2) Å3, andZ = 4. Least-squares refinement of 3632 reflections gave a final agreement factor ofR = 0.0603 (R w = 0.0802). Compound4 crystallizes in the monoclinic space group C2/c with unit cell parametersa = 13.915(7) Å,b = 14.718(6) Å,c = 17.109(6) Å,β = 100.44(3)°,V = 3446(5) Å3, andZ = 8. Least-squares refinement of 2910 reflections gave a final agreement factor ofR = 0.0763 (R w = 0.0863). Plenum Publishing Corporation, 1996 Azam Kazi Department of Chemistry, Jahangirnagar University, 1342, Savar, Dhaka, Bangladesh aut Dilshad Rahima Department of Chemistry, Jahangirnagar University, 1342, Savar, Dhaka, Bangladesh aut Kabir Shariff Department of Chemistry, Jahangirnagar University, 1342, Savar, Dhaka, Bangladesh aut Miah Rashid Department of Chemistry, Jahangirnagar University, 1342, Savar, Dhaka, Bangladesh aut Shahiduzzaman Mohammad Department of Chemistry, Jahangirnagar University, 1342, Savar, Dhaka, Bangladesh aut Rosenberg Edward Department of Chemistry, The University of Montana, 59812, Missoula, MT aut Hardcastle Kenneth Department of Chemistry, California State University, 91330, Northridge, CA aut Hursthouse Michael School of Chemistry and Applied Chemistry, University of Wales Cardiff, CF1 3TB, Cardiff, UK aut Abdul Malik K. School of Chemistry and Applied Chemistry, University of Wales Cardiff, CF1 3TB, Cardiff, UK aut Journal of Cluster Science Kluwer Academic Publishers-Plenum Publishers 7/1(1996-03-01), 49-70 1040-7278 7:1<49 1996 7 10876 https://doi.org/10.1007/BF01166176 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF01166176 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Azam Kazi Department of Chemistry, Jahangirnagar University, 1342, Savar, Dhaka, Bangladesh aut NATIONALLICENCE 700 1- Dilshad Rahima Department of Chemistry, Jahangirnagar University, 1342, Savar, Dhaka, Bangladesh aut NATIONALLICENCE 700 1- Kabir Shariff Department of Chemistry, Jahangirnagar University, 1342, Savar, Dhaka, Bangladesh aut NATIONALLICENCE 700 1- Miah Rashid Department of Chemistry, Jahangirnagar University, 1342, Savar, Dhaka, Bangladesh aut NATIONALLICENCE 700 1- Shahiduzzaman Mohammad Department of Chemistry, Jahangirnagar University, 1342, Savar, Dhaka, Bangladesh aut NATIONALLICENCE 700 1- Rosenberg Edward Department of Chemistry, The University of Montana, 59812, Missoula, MT aut NATIONALLICENCE 700 1- Hardcastle Kenneth Department of Chemistry, California State University, 91330, Northridge, CA aut NATIONALLICENCE 700 1- Hursthouse Michael School of Chemistry and Applied Chemistry, University of Wales Cardiff, CF1 3TB, Cardiff, UK aut NATIONALLICENCE 700 1- Abdul Malik K. School of Chemistry and Applied Chemistry, University of Wales Cardiff, CF1 3TB, Cardiff, UK aut NATIONALLICENCE 773 0- Journal of Cluster Science Kluwer Academic Publishers-Plenum Publishers 7/1(1996-03-01), 49-70 1040-7278 7:1<49 1996 7 10876 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer