The first thiolate-bridged dinuclear indacarboranes with sigma-coordination

The good yield preparation and the structural analysis of three novel thiolate-bridged dinuclear sigma-bonded indacarboranes [(C2B9H11)In-III{S(CH2)(2)S(CH2)(2)S}](2).(BkNMe3)(2) (2 .(BzNMe(3))(2)), [(C2B9H11)In-III(SPh)(2)](2). PPN2 (3 . (PPN2)), and [(C2B9H11)In-III(SCH2CH2S)](2).(PPh3-p-xylyl-PPh3) (4(PPh3-p-xylyl-PPh3)) which constitute the first examples of dimeric thiolatoindacarboranes are reported. The complex 2 (BzNMe3) was prepared by reacting [(C2B9H11)InCl2(THF)].(BzNMe(3)) with sodium salt of bis-2-mercaptoethyl sulfide. The other two compounds were synthesized by utilizing the reactivity of indiumhalothiolate with Tl-2(C2B9H11) in the presence of a suitable countercation. All three compounds crystallize in the triclinic space group P (1) over bar. Other crystallo graphic data are given in the order of the compound: unit cell parameters, V; Z; unique data (F-o > 4.0 sigma(F-o)); R-1. 2 .(BzNMe(3))(2): a = 8.608(2) Angstrom, b = 11.886(3) Angstrom, c = 13.283(4)Angstrom, alpha = 79.39(2)degrees, beta = 76.71(2)degrees, gamma = 73.82(2)degrees, 1259.7(6) Angstrom(3); 1; 2489; 4.45%. 3 .(PPN)(2): a =11.664(4) Angstrom, b = 11.981(4) Angstrom, c=18.454(6) Angstrom, alpha= 82.66(2)degrees, beta = 81.03(2)degrees, gamma= 86.22(2)degrees; 2523.7(15) Angstrom(3); 1; 5682; 4.50%. 4 (PPh3-p-xylyl-PPh3): a 10.605(1) Angstrom, b=12.088(2) Angstrom, c 12.923(2) Angstrom, alpha = 103.51(1)degrees, beta = 94.37(1)degrees gamma = 105.83(2)degrees; 1532.3(4) Angstrom(3); 1; 2776; 4.13%. For all three compounds, the dimeric nature centers around a crystallographic inversion center, resulting in the rhomboid InSInS core with the S-In-S angle being acute for 2 and 3 while obtuse for 4 and the two bridging thiolate groups are arranged in anti-position across the planar InSInS rhomboid. All indium metal centers basically adopt distorted tetrahedral geometry with two bridging sulfur atoms, one terminal sulfur atom, and the unique boron atom although two additional weak coordinations to the indium center from the sulfide sulfur atom and the cage boron atom adjacent to the unique boron are conceivable in the case of complex 2. In all cases, the extreme "slip distortion" of the indium center toward the unique boron atom occurs, resulting in the interaction of the InS3 moiety with the nido-C2B9 cage via the sigma-In-B10 bond in endo-fashion.
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INORGANIC CHEMISTRY, v.38, no.2, pp.353 - 357

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CH-Journal Papers(저널논문)
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