Bis(thiophosphinoyl)amines and their neutral cobalt(II) complexes, containing stable tetrahedral CoS4 cores.: Crystal structures of NH(SPMe2)(SPPh2) and [Co{(SPMe2)(SPPh2)N}2]

被引:43
作者
Silvestru, C [1 ]
Rosler, R
Drake, JE
Yang, JC
Espinosa-Perez, G
Haiduc, I
机构
[1] Univ Babes Bolyai, Fac Chim, RO-3400 Cluj Napoca, Romania
[2] Univ Windsor, Dept Chem & Biochem, Windsor, ON N9B 3P4, Canada
[3] Univ Nacl Autonoma Mexico, Inst Quim, Mexico City 04510, DF, Mexico
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1998年 / 01期
关键词
D O I
10.1039/a705086k
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The compound NH(SPMe2)(SPPh2) was prepared using a new method, ie. the reaction between Li[HN(S)PPh2] and Me2P(S)Cl in a diethyl ether-n-hexane mixture. The complex [Co{(SPMe2)(SPPh2)N}(2)] was obtained by the reaction of CoCl2 . 6H(2)O and K[(SPMe2)(SPPh2)N] in methanol. The crystal and molecular structure of both the free acid NH(SPMe2)(SPPh2) and its cobalt (II) complex [Co{(SPMe2)(SPPh2)(2)N}(2)] were determined using X-ray diffractometry. The acid exhibits an anti conformation of the sulfur atoms in the SPNPS system and dimeric pairs are formed in the crystal through N(1)-H(1)... S(2a) [2.43(9) Angstrom] hydrogen bonds, which involve only the sulfur atom of the S=PPh2 group of each molecule. The cobalt complex consists of discrete, monomeric molecules, with isobidentate ligands [average Co-S 2.32(1), average P-S 2.031(5) Angstrom] and a distorted tetrahedral CoS4 core (S-Co-S range 102.7-117.7 degrees). The structures of both the free acid and its cobalt (II) derivative are discussed in relation with other bis(thiophosphinoyl)amines and metal complexes containing a CoS4 core.
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页码:73 / 78
页数:6
相关论文
共 29 条
[1]   SQUARE-PLANAR COMPLEXES OF PENTANE-2,4-DITHIONE (DITHIOACETYLACETONE) - CRYSTAL-STRUCTURES OF COBALT(II) AND NICKEL(II) DERIVATIVES [J].
BECKETT, R ;
HOSKINS, BF .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1974, (06) :622-625
[2]   POLYHEDRON REPORT NUMBER-56 - BIS(DIPHENYLPHOSPHINO)AMINE AND RELATED CHEMISTRY [J].
BHATTACHARYYA, P ;
WOOLLINS, JD .
POLYHEDRON, 1995, 14 (23-24) :3367-3388
[3]   BIS(BIDENTATE) COMPLEXES OF IMINOBIS(DIPHENYLPHOSPHINE CHALCOGENIDES) [M(N(XPPH(2))(2)-X,X')(2)] (X=S OR SE M=NI, PD OR PT) [J].
BHATTACHARYYA, P ;
NOVOSAD, J ;
PHILLIPS, J ;
SLAWIN, AMZ ;
WILLIAMS, DJ ;
WOOLLINS, JD .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1995, (10) :1607-1613
[4]  
BUCKINGHAM DA, 1987, COMPREHENSIVE COORDI, V4, P870
[5]   MODELS OF LYSINE CYSTEINE HYDROGEN-BONDING IN METALLOTHIONEIN - HYDROGEN-BONDING BETWEEN AMMONIUM AND BENZENETHIOLATE IN [(C6H11)2NH2]2[CO(SC6H5)4] [J].
CHUNG, WP ;
DEWAN, JC ;
WALTERS, MA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (02) :525-530
[6]   PREPARATION AND CRYSTAL STRUCTURE OF A STERICALLY UNENCUMBERED TETRAHEDRAL CHELATE COMPLEX CONTAINING A NIS4 CORE, [SPME2NPME2S]2NI2 [J].
CHURCHILL, MR ;
COOKE, J ;
WORMALD, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1969, 91 (23) :6518-+
[7]   CRYSTAL STRUCTURE OF BIS(IMIDOTETRAMETHYLDITHIODIPHOSPHINO-S,S)NICKEL(II), A TETRAHEDRAL COMPLEX WITH AN NIS4 CORE [J].
CHURCHILL, MR ;
COOKE, J ;
FENNESSEY, JP ;
WORMALD, J .
INORGANIC CHEMISTRY, 1971, 10 (05) :1031-+
[8]   TETRAKIS(N,N'-DIETHYLTHIOUREA)COBALT(II) DIPERCHLORATE [J].
FAWCETT, TG ;
FEHSKENS, EE ;
POTENZA, JA ;
SCHUGAR, HJ ;
LALANCETTE, RA .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 1979, 35 (JUN) :1460-1463
[9]   EFFECTS OF CO-S TORSION ANGLE VARIATION IN A COBALT(II)-THIOLATE COMPLEX - X-RAY CRYSTAL-STRUCTURE ANALYSIS, SINGLE-CRYSTAL EPR MEASUREMENTS AND LIGAND-FIELD CALCULATIONS [J].
FUKUI, K ;
MASUDA, H ;
OHYANISHIGUCHI, H ;
KAMADA, H .
INORGANICA CHIMICA ACTA, 1995, 238 (1-2) :73-81
[10]   INORGANIC (CARBON-FREE) CHELATE RINGS [J].
HAIDUC, I ;
SILAGHIDUMITRESCU, I .
COORDINATION CHEMISTRY REVIEWS, 1986, 74 :127-270