Synthesis and crystal structure of a novel binuclear copper(I) complex with bridging monohydrogensulfido (SH) ligands

A novel dinuclear copper(I) complex, [Cu₂(μ₂-SH)₂(PPh₃)₃] (1) (PPh₃ = triphenylphosphine) has been prepared by the reaction of CuCl with triphenylphosphine and mercaptopropanoic acid (MPA) mixed in the ratio of 1:1:1. In the molecular structure of 1, two copper atoms are bridged by S atoms of two monohydrogensulfido anions forming a four-membered ring. The planar Cu₂S₂ core is characterized by significant cuprophilic interactions (Cu-Cu distance = 2.897 ?). One copper atom in 1 is coordinated with two sulfur atoms and one phosphorus atom of PPh₃ adopting a trigonal planar geometry, while the coordination environment around the other copper center is distorted tetrahedral that is completed by two sulfur atoms of SH groups and two phosphorus atoms of PPh₃ molecules.     

Synthesis, spectroscopic characterization and structural studies of chloro dioxotriphenylphosphine oxide (O,O-dialkyl/diphenyl(alkylene)dithiophosphate) molybdenum(VI) complexes: crystal structure of MoO2Cl2(OSMe2)2

Reactions of dichlorodioxobis(triphenylphosphine oxide)molybdenum(VI) complexes with ammonium/sodium salts of O,O-dialkyl(alkylene) and diphenyl dithiophosphoric acids in 1:1 molar ratio in dichloromethane solution yield dioxomolybdenum complexes of the types, MoO₂Cl[S₂P(OR)₂] · OPPh₃ (R=Me, Et, i-Pr, Ph) and MoO₂Cl[S₂] · OPPh₃. (G=-CH₂CMe₂CH₂O-, -OCMe₂CMe₂O-). These newly synthesized compounds were characterized by IR, UV-visible and ¹H NMR spectroscopy and elemental analysis. The molecular structure of MoO₂Cl₂(OSMe₂)₂ was determined by single-crystal X-ray diffraction. MoO₂Cl₂(OSMe₂)₂ crystallizes as orthorhombic in the space group Pbca with cell parameters a=13.7235(3) Å, b=12.2429(2) Å, c=14.3356(3) Å, V=2408.60(8) Å⁻³, Z=8, R=0.0221, R_w=0.0519. There are two cis oxo ligands, two cis dimethylsulphoxide moieties and two trans chlorine atoms in a distorted octahedral environment around molybdenum.     

Silver(I) complexes with heterocyclic thiones and tertiary phosphines as ligands. Part 4. Dinuclear complexes of silver(I) bromide: the crystal structure of bis[bromo-(pyrimidine-2-thione)(triphenylphosphine)silver(I)]

Mixed-ligand complexes of the formula [Ag(PPh₃)(L)Br]₂ were obtained by treatment of various heterocyclic thiones L {L=pyridine-2-thione (py2SH), pyrimidine-2-thione (pymtH), benz-1,3-imidazoline-2-thione (bzimtH₂), benz-1,3-thiazoline-2-thione (bztztH), 1-methyl-1,3-imidazoline-2-thione (meimtH) and 5-methoxy-benz-1,3-imidazoline-2-thione (5MeObzimtH₂)} with equivalent quantities of silver(I) bromide and triphenylphosphine in dry acetone. The compounds were characterized by their IR, far-IR, UV–Vis and ¹H NMR spectroscopic data. The crystal structure of [Ag(PPh₃)(pymtH)Br]₂ was determined by single-crystal X-ray diffraction methods. The complex exhibits a planar Ag₂Br₂ moiety in which each of the doubly bromine-bridged Ag(I) centres is further bonded to one phosphine P and one thione S atom.     

Complexes of N-thiophosphorylthioureas RNHC(S)NHP(S)(OiPr)2 (HL) (R = pyridin-2-yl, pyridin-3-yl, 6-amino-pyridin-2-yl) with copper(I): Crystal structures of Cu(PPh3)nL (n = 1, 2)

Reaction of the potassium salts of N-thiophosphorylated thioureas of common formula RNHC(S)NHP(S)(OiPr)₂ [R = pyridin-2-yl (HL^a), pyridin-3-yl (HL^b), 6-amino-pyridin-2-yl (HL^c)] with Cu(PPh₃)₃I in aqueous EtOH/CH₂Cl₂ leads to mononuclear [Cu(PPh₃)₂L^a,b-S,S′] (1, 2) and [Cu(PPh₃)L^c-S,S′] (3) complexes. Using copper(I) iodide instead of Cu(PPh₃)₃I, polynuclear complexes [Cu_n(L-S,S′)_n] (4-6) were obtained. The structures of these compounds were investigated by IR, ¹H, ³¹P{¹H} NMR spectroscopy, ES-MS and elemental analyses. The crystal structures of Cu(PPh₃)₂L^b (2) and Cu(PPh₃)L^c (3) were determined by single-crystal X-ray diffraction.     

Copper(I) complexes of N-thioacylamido(thio)phosphates and triphenylphosphine

Heteroligand copper(I) complexes of bi- or bis-bidentate acylamidophosphates PhC(S)NHP(S)(OPr-i)₂, PhC(S)NHP(O)(OPr-i)₂, Et₂NC(S)NHP(S)(OPr-i)₂, PhNHC(S)NHP(S)(OPr-i)₂, N-(4-aminobenzo-15-crown-5)-C(S)NHP(S)(OPr-i)₂, N,N-(1,10-diaza-18-crown-6)-[C(S)NHP(S)(OPr-i)₂]₂, and triphenylphosphine were prepared and characterised. Copper is bound by two PPh₃ and one SCNPX (X = O, S) fragment of chelating ligand in all cases. Triphenylphosphine molecules reversibly dissociate in solution. Details of the X-ray structures of (Ph₃P)₂Cu[PhC(S)NP(S)(OPr-i)₂] and (Ph₃P)₂Cu[Et₂NC(S)NP(S)(OPr-i)₂] are reported.     

Half-sandwich ruthenium thiocarbonate complexes: Structures of CpRu(PPh3)2SCO2Bu, CpRu(dppe)SCO2Bu and CpRu(PPh3)(CO)SCO2Bu

Thiocarbonate ruthenium complexes of the form CpRu(L)(L′)SCO₂R (L = L′ = PPh₃ (1), 1/2 dppe (2), L = PPh₃, L′ = CO (3); R = Et (a), Buⁿ (b), C₆H₅ (c), 4-C₆H₄NO₂ (d)) have been synthesized by the reaction of the corresponding sulfhydryl complexes, CpRu(L)(L′)SH, with chloroformates, ROCOCl, at low temperature. The bis(triphenylphosphine) complexes 1 can be converted to 3 under CO atmosphere. The crystal structures of CpRu(PPh₃)₂SCO₂Buⁿ (1b), CpRu(dppe)SCO₂Buⁿ (2b), and CpRu(PPh₃)(CO)SCO₂Buⁿ (3b) are reported.