Synthesis and Characterization of Zinc and Cadmium Compounds with Arenephosphinothiol Ligands. Crystal and Molecular Structures of [Cd2{2-(Ph2PO)C6H4S}
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- 作者：Paulo Pé ; rez-Lourido ; Jaime Romero ; José ; A. Garcí ; a-Vá ; zquez ; Antonio Sousa ; Kevin P. Maresca ; and Jon Zubieta
- 刊名：Inorganic Chemistry
- 出版年：1999
- 出版时间：August 9, 1999
- 年：1999
- 卷：38
- 期：16
- 页码：3709 - 3715
- 全文大小：108K
- 年卷期：v.38,no.16(August 9, 1999)
- ISSN：1520-510X
文摘
The electrochemical oxidation of a metallic anode (zinc or cadmium) in an acetonitrile solution of a series ofarenephosphinothiol ligands, 2-(Ph2P)C6H4SH, 2-(Ph2P)-6-(Me3Si)C6H3SH, 2-(Ph2PO)-6-(Me3Si)C6H3SH, and PhP(C6H4SH-2)2 [abbreviated RP-(SH)x, x = 1 or 2], affords [M(RP-S)2] and [M(RP-S2)], M = Zn, Cd. Adducts ofseveral of these compounds with 1,10-phenanthroline and 2,2'-bipyridine have also been obtained by addition ofthese coligands to the electrolysis phase. The compounds obtained have been characterized by microanalysis, IR,UV-visible, FAB spectrometry and 1H, 31P NMR spectroscopic studies. The compounds, [Cd2{2-(Ph2PO)C6H4S}4]CH3CN (1), [Zn{2-(Ph2P)-6-(Me3Si)C6H3S}2] (2), [Cd{2-(Ph2PO)-6-(Me3Si)C6H3S}2(CH3OH)] (3), and[Zn{PhPO(C6H4S-2)2}(bipy)] (4), have been also characterized by single-crystal X-ray diffraction. Compound 1is binuclear with a {Cd2S2} core and distorted trigonal bipyramidal {CdO2S3} geometry about the Cd sites.Compounds 2, 3, and 4 are mononuclear with distorted tetrahedral {ZnP2S2}, distorted square pyramidal {CdO3S2},and distorted trigonal bipyramidal {ZnON2S2} geometries, respectively. Crystal data: 1, C42H37N3O2P2S2Cd,triclinic, P
, a = 13.5780(2) Å, b = 13.8505(2) Å, c = 13.9526(2) Å, 
= 106.622(1)
, 
= 109.693(1), 
=107.137(1), V = 2133.30(5) Å3, Z = 2, 9560 reflections, R = 0.0483; 2, C46H50N2P2S2Si2Zn, monoclinic, C2/c,a = 21.332(4) Å, b = 9.391(2) Å, c = 25.938(5) Å, = 113.84(3), V = 4753(2) Å3, Z = 4, 2564 reflections,R = 0.0377; 3, C43H48CdO3P2S2Si2, triclinic, P, a = 12.1237(4) Å, b = 14.0568(4) Å, c = 15.0938(2) Å, =70.836(2), = 83.410(2), = 65.397(2), V = 2208.7(1) Å3, Z = 2, 4936 reflections, R = 0.0738; 4, C29H22Cl3N2OP2S2Zn, triclinic, P, a = 8.9556(3) Å, b = 12.7911(4) Å, c = 14.0598(5) Å, = 82.671(1), =73.140(1), = 74.113(1), V = 1480.44(9)(1) Å3, Z = 2, 3820 reflections, R = 0.0511.
, a = 13.5780(2) Å, b = 13.8505(2) Å, c = 13.9526(2) Å, = 106.622(1), = 109.693(1), =107.137(1), V = 2133.30(5) Å3, Z = 2, 9560 reflections, R = 0.0483; 2, C46H50N2P2S2Si2Zn, monoclinic, C2/c,a = 21.332(4) Å, b = 9.391(2) Å, c = 25.938(5) Å, = 113.84(3), V = 4753(2) Å3, Z = 4, 2564 reflections,R = 0.0377; 3, C43H48CdO3P2S2Si2, triclinic, P, a = 12.1237(4) Å, b = 14.0568(4) Å, c = 15.0938(2) Å, =70.836(2), = 83.410(2), = 65.397(2), V = 2208.7(1) Å3, Z = 2, 4936 reflections, R = 0.0738; 4, C29H22Cl3N2OP2S2Zn, triclinic, P, a = 8.9556(3) Å, b = 12.7911(4) Å, c = 14.0598(5) Å, = 82.671(1), =73.140(1), = 74.113(1), V = 1480.44(9)(1) Å3, Z = 2, 3820 reflections, R = 0.0511.