- Reactivity of copper(I) tetrahydroborates toward CS2 and SCNPh. Structures of (PPh3)2Cu(μ-S2CSCH2SCS 2)Cu(PPh3)2, (PPh3)2Cu(S2COEt), and (PPh3)2Cu(S2CNHPh)·CHCl3
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The reactivity of the copper(I) tetrahydroborate complexes (PPh3)2Cu(BH4) (1), (PCy3)2Cu(BH4) (2), (triphos)Cu(BH4) (3) [triphos = 1,1,1-tris((diphenylphosphino)methyl)ethane], and (np3)Cu(BH4) (4) [np3 = tris(2-(diphenylphosphino)ethyl)amine] toward CS2 and SCNPh has been investigated. Compound 1 reacts with CS2 to give the dinuclear copper(I) complex (PPh3)2Cu(μ-S2CSCH2SCS 2)Cu(PPh3)2 (6), whose molecular structure has been established by single-crystal X-ray diffraction methods. Crystal data: C75H62Cu2P4S6, monoclinic, space group C2/c, Z = 8, a = 53.573 (30) A?, b = 12.759 (9) A?, c = 22.856 (15) A?, β = 104.6 (1)°, final R factor of 0.092 for 4573 observed reflections. In the dimeric molecule, two (PPh3)2Cu fragments are held together by a bridging S2CSCH2SCS22- ligand, formed from a double head-to-tail condensation of three CS2 molecules. The crystal structure of the xanthate complex (PPh3)2Cu(η2-S2COEt) (7) obtained by the solvolysis of 6 in CH2Cl2/ethanol has been determined. Crystal data: C39H35CuOP2S2, monoclinic, space group P21/n, Z = 4, a = 20.299 (14) A?, b = 18.636 (12) A?, c = 9.282 (8) A?, β = 95.5 (1)°, final R factor of 0.052 for 2660 observed reflections. Dithioformate complexes are obtained when 3 and 4 are reacted with CS2. Phenyl isothiocyanate reacts with the present copper(I) tetrahydroborates to give the corresponding N-phenyldithiocarbamate complexes. The crystal structure of (PPh3)2Cu(η2-S 2CNHPh)·CHCl3 (10) has been determined. Crystal data: C44H37Cl3CuNP2S2, triclinic, space group P1, Z = 2, a = 14.772 (11) A?, b = 13.105 (11) A?, c = 12.332 (9) A?, α = 115.9 (1)°, β = 97.1 (1)°, γ = 95.7 (1)°, final R factor of 0.070 for 3635 observed reflections.
- Bianchini, Claudio,Ghilardi, Carlo A.,Meli, Andrea,Midollini, Stefano,Orlandini, Annabella
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p. 932 - 939
(2008/10/08)
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