BINDING OF BIVALENT AND TRI-VALENT NICKEL BY AZOPHENOLATES INCORPORATING THIOETHER ETHER DONOR SITES

被引:23
作者
CHOUDHURY, SB [1 ]
RAY, D [1 ]
CHAKRAVORTY, A [1 ]
机构
[1] INDIAN ASSOC CULTIVAT SCI,DEPT INORGAN CHEM,CALCUTTA 700032,W BENGAL,INDIA
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1992年 / 01期
关键词
D O I
10.1039/dt9920000107
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Nickel(II) complexes of tri- and hexa-dentate ligands in which the donors are azo nitrogen, phenolic oxygen and thioether sulfur or ether oxygen have been isolated. Structure determination of three complexes has established the presence of distorted octahedral NiN2O2X2 (X = S or O) co-ordination spheres. In dichloromethane solution the nickel(III)-nickel(II) couple is electrochemically observable for the thioether complexes with E1/2 in the range 0.65-0.85 V vs. saturated calomel electrode. The blue-violet nickel(III) species can be quantitatively electrogenerated in solution. Upon freezing (77 K) axial EPR spectra (g parallel-to almost-equal-to 2.18, g perpendicular-to almost-equal-to 2.06) compatible with the uncommon hole configuration (d(x2-y2))1 are observed. The ether complexes are more difficult to oxidise and the nickel(III) species are not tractable. This is consistent with the higher strength of nickel-thioether compared to -ether binding.
引用
收藏
页码:107 / 112
页数:6
相关论文
共 30 条
[1]  
AVDEEF A, 1970, J AM CHEM SOC, V92, P6972
[2]   CHEMISTRY OF FERROVERDINS AND FERRIVERDINS - IRON REDOX AND GEOMETRICAL STEREODYNAMISM [J].
BASU, P ;
CHOUDHURY, SB ;
PAL, S ;
CHAKRAVORTY, A .
INORGANIC CHEMISTRY, 1989, 28 (13) :2680-2686
[3]   CHEMISTRY OF THIOETHER MACROCYCLIC COMPLEXES [J].
Blake, Alexander J. ;
Schroeder, Martin .
ADVANCES IN INORGANIC CHEMISTRY <D>, 1990, 35 :1-80
[4]   NICKEL IN METALLOPROTEINS [J].
CAMMACK, R .
ADVANCES IN INORGANIC CHEMISTRY, 1988, 32 :297-333
[5]   NICKEL(III)-SULFUR BINDING - CHEMISTRY OF THE TRIS(XANTHATE) FAMILY [J].
CHOUDHURY, SB ;
RAY, D ;
CHAKRAVORTY, A .
INORGANIC CHEMISTRY, 1990, 29 (23) :4603-4611
[6]   CROWN THIOETHER CHEMISTRY - HOMOLEPTIC HEXAKIS(THIOETHER) COMPLEXES OF NICKEL(II) [J].
COOPER, SR ;
RAWLE, SC ;
HARTMAN, JR ;
HINTSA, EJ ;
ADMANS, GA .
INORGANIC CHEMISTRY, 1988, 27 (07) :1209-1214
[7]   SEXADENTATE CHELATE COMPOUNDS .7. [J].
DWYER, FP ;
GILL, NS ;
GYARFAS, EC ;
LIONS, F .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1954, 76 (02) :383-386
[8]   STABILIZATION OF TRIVALENT NICKEL THROUGH 1-2 COORDINATION BY CYCLIC TERDENTATE LIGANDS CH2CH2NH(CH2)2NH(CH2)2X(X = NH, O, OR S) [J].
FABBRIZZI, L ;
PROSERPIO, DM .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1989, (02) :229-232
[9]   SYNTHESIS OF A NOVEL MACROBICYCLIC LIGAND, 15-THIA-1,5,8,12-TETRAAZABICYCLO[10.5.2]NONADECANE, AND ITS NICKEL(II) AND COPPER(II) COMPLEXES - X-RAY CRYSTAL-STRUCTURES OF [CU(L1)](CLO4)2 AND [NI(L1)(CLO4)]CLO4 [J].
FORTIER, DG ;
MCAULEY, A .
INORGANIC CHEMISTRY, 1989, 28 (04) :655-662
[10]   VIABILITY OF THE [NIIII(SR)4]- UNIT IN CLASSICAL COORDINATION-COMPOUNDS AND IN THE NICKEL SULFUR CENTER OF HYDROGENASES [J].
FOX, S ;
WANG, Y ;
SILVER, A ;
MILLAR, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (08) :3218-3220