Paulo Pérez-Lourido

Electrochemical synthesis and crystal structure of silver(I) complexes with some heterocyclic thiones

Two silver(I) complexes, [{Ag(SR)}6][R1SH = 6-(tert-butyldimethylsilyl)pyridine-2-thione 1, R2SH = 3,6-bis(tert-butyldimethylsilyl)pyridine-2-thione 2], have been synthesized by electrochemical oxidation of the metal in an acetonitrile solution of the neutral heterocyclic thiones. The reaction of equimolar amounts of dppm [bis(diphenylphosphino)methane] with complexes 1 and 2 in dichloromethane resulted in the formation of [Ag4Cl4(dppm)2]3 and the elimination of RSCH2SR. Single-crystal X-ray analyses were performed for compounds 1, 3 and R2SCH2SR2.

Zinc(II), cadmium(II), mercury(II), and ethylmercury(II) complexes of phosphinothiol ligands.

Neutral zinc, cadmium, mercury(II), and ethylmercury(II) complexes of a series of phosphinothiol ligands, PhnP(C6H3(SH-2)(R-3))3-n (n = 1, 2; R = H, SiMe3) have been synthesized and characterized by IR and NMR ((1)H, (13)C, and (31)P) spectroscopy, FAB mass spectrometry, and X-ray structural analysis. The compounds [Zn{PhP(C6H4S-2)2}] (1) and [Cd{Ph2PC6H4S-2}2] (2) have been synthesized by electrochemical oxidation of anodic metal (zinc or cadmium) in an acetonitrile solution of the appropriate ligand. The presence of pyridine in the electrolytic cell affords the mixed complexes [Zn{PhP(C6H4S-2)2}(py)] (3) and [Cd{PhP(C6H4S-2)2}(py)] (4). [Hg{Ph2PC6H4S-2}2] (5) and [Hg{Ph2PC6H3(S-2)(SiMe3-3)}2] (6) were obtained by the addition of the appropriate ligand to a solution of mercury(II) acetate in methanol in the presence of triethylamine. [EtHg{Ph2PC6H4S-2}] (7), [EtHg{Ph2P(O)C6H3(S-2)(SiMe3-3)}] (8), [{EtHg}2{PhP(C6H4S-2)2}] (9), and [{EtHg}2{PhP(C6H3(S-2)(SiMe3-3))2}] (10) were obtained by reaction of ethylmercury(II) chloride with the corresponding ligand in methanol. In addition, in the reactions of EtHgCl with Ph2PC6H4SH-2 and with the potentially tridentate ligand PhP(C6H3(SH-2)(SiMe3-3)) 2, cleavage of the Hg-C bond was observed with the formation of [Hg{Ph2PC6H4S-2}2] (5) and [Hg(EtHg) 2{PhP(O)(C6H3(S-2)(SiMe3-3))2}2] (11), respectively, and the corresponding hydrocarbon. The crystal structures of [Zn3{PhP(C6H4S-2)2}2{PhP(O)(C6H4S-2)2}] (1*), [Cd2{Ph2PC6H4S-2}3{Ph2P(O)C6H4S-2}] (2*), 3, 5, 6, [EtHg{Ph2P(O)C6H4S-2}] (7*), 8, 9, [{EtHg}2{PhP(O)(C6H3(S-2)(SiMe3-3))2}] (10*), and 11 are discussed. The molecular structures of 1, 2, 4, 7, and 10 have also been studied by means of density functional theory (DFT) calculations.

Synthesis and characterisation of cobalt and nickel compounds with phosphinothiol ligands. Crystal and molecular structures of [Co{ {2- (Ph2P)-6- (Me3Si)C6H3S)} }3], [Ni{ {2- (Ph2P)-6- (Me3Si)C6H3S)} }2] and [Co{ {2- (Ph2PO)-6- (Me3Si)C6H3S} }2]

Abstract Theelectrochemical oxidation of anodic metal (cobalt or nickel) in an acetonitrile solution of phosphinothiol ligands, 2- (Ph2P)C6H4SH, 2- (Ph2P)-6- (SiMe3)C6H3SH, 2- (Ph2PO)-6- (SiMe3)C6H3SH, affords [Co{2- (Ph2P)C6H4S)}3] 1, [Ni{2- (Ph2P)C6H4S}2] 2, [Co{2- (Ph2P)-6- (SiMe3)C6H3S}3] 3, [Ni{2- (Ph2P)-6- (SiMe3) C6H3S}2] 4, [Co{2- (Ph2PO)-6- (SiMe3)C6H3S}2] 5, [Co{2- (Ph2PO)-6- (SiMe3)C6H3S}3] 6 and [Ni{2- (Ph2PO)-6- (SiMe3)C6H3S}2] 7. All compounds have been characterised by microanalysis, IR, UV-visible, FAB and NMR spectroscopic studies and compounds 3, 4 and 5 by single-crystal X-ray diffraction.

Complexes of copper(I), silver(I), nickel(II) and cadmium(II) with 6-tert-butyldimethylsilylpyridine-2-thionate (6-ButSidmepyS−): crystal structure of [Cu2(6-ButSidmepyS)2dppm2]

Complexes of general formulae [M(6-Bu t SidmepyS)] (M = Cu, Ag] or [ M (6- Bu t SidmepyS ) 2 ] (M = Ni, Cd) were prepared by electrochemical oxidation of the appropriate metal in an acetonitrile solution of the neutral heterocyclic thione (6-Bu t SidmepySH): with a solution of the thione and 2,2′-bipyridine (bipy) this method gives [Ni(6-Bu t SidmepyS) 2 bipy]. The reaction between [Cu(6-Bu t SidmepyS)] and 1,2-bis(diphenylphosphino)ethane (dppe) or bis(diphenylphosphino)methane (dppm) in acetonitrile yielded [Cu 2 (6-Bu t SidmepyS) 2 (dppe) 2 ] and [Cu 2 (6-Bu t SidmepyS) 2 (dppm) 2 ]: the latter exhibits a dinuclear structure with one dppm and two thione ligands acting as bridges between the copper atoms. Vibrational and 1 H and 13 C NMR spectra of the complexes are discussed and related to the structure.

MOLECULAR STRUCTURE OF A FIVE-COORDINATE BINUCLEAR ZINC COMPLEX

Abstract The structure of the title compound, [Zn 2 (C 25 H 17 NO 2 PS) 2 Cl 2 ], consists of binuclear molecules with phenol oxygen atoms bridging the zinc atoms. Each metal is in a distorted trigonal bipyramidal [ZnNO 3 Cl] environment.