Bis(pyridine-N)(7,8,17,18-tetracyano-5,10,15,20-tetraphenylporphyrinato)-nickel(N) dimethanol solvate

被引:15
作者
Duval, H
Bulach, V
Fisher, J
Weiss, R
机构
[1] Lab. Cristallochimie Chim. Struct., Université Louis Pasteur, Institut Lebel, 67070 Strasbourg Cedex, 4, rue Blaise Pascal
关键词
D O I
10.1107/S0108270197003995
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The title compound, [Ni(C48H24N8)(C5H5N)(2)].2CH(4)O, is a high-spin bis(pyridine)-Ni-II derivative of an antipodally beta-pyrrole-tetracyano-substituted meso-tetraphenylporphyrin. The [Ni(py)2{tpp(CN)(4)}] molecule [py is pyridine and tpp(CN)(4) is 7,8,17,18-tetracyano-5,10,15,20-tetraphenylporphyrinato] lies on a crystallographic centre of symmetry, but its non-crystallographic symmetry is close to D-2h. The core of the tpp(CN)(4), porphyrin dianion is essentially planar. The high-spin state of the Ni-II cation leads to a lengthening of the Ni-N(pyrrole) bond distances relative to those present in the low-spin [Ni(II)tpp] derivative. Moreover, the electron-withdrawing beta-pyrrole cyano substituents, which lie in the antipodal pyrrolic rings, cause an increase in the C7-C8 and the antipodal C7'-C8' bond distances as well as an opening of the C6-N2-C9 and the antipodal C6'-N2'-C9' bond angles.
引用
收藏
页码:1027 / 1029
页数:3
相关论文
共 11 条
[1]  
CALLOT HJ, 1974, B SOC CHIM FR II-CH, P1492
[2]   STEREOCHEMISTRY OF LOW-SPIN IRON PORPHYRINS .1. BIS(IMIDAZOLE)-ALPHA,BETA,GAMMA,DELTA-TETRAPHENYLPORPHINATOIRON(III) CHLORIDE [J].
COLLINS, DM ;
COUNTRYMAN, R ;
HOARD, JL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (06) :2066-+
[3]   REGIOSPECIFIC INTRODUCTION OF 4 SUBSTITUENTS TO PORPHYRIN SYSTEMS AT ANTIPODAL PYRROLENIC POSITIONS [J].
CROSSLEY, MJ ;
BURN, PL ;
CHEW, SS ;
CUTTANCE, FB ;
NEWSOM, IA .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1991, (21) :1564-1566
[4]  
*ENR NON, 1977, CAD 4 OP MAN
[5]  
FAIR CK, 1990, MOIEN INTERACTIVE IN
[6]   EFFECTS OF BETA-SUBSTITUTIONS ON THE AXIAL COMPLEXATION OF NI(II)TPP BY THE LEWIS-BASES [J].
GIRAUDEAU, A ;
GROSS, M ;
CALLOT, HJ .
ELECTROCHIMICA ACTA, 1981, 26 (12) :1839-1843
[7]  
Johnson C. K., 1976, ORNL5138
[8]   MOLECULAR STEREOCHEMISTRY OF A 6-COORDINATE NICKEL(II) PORPHYRIN [J].
KIRNER, JF ;
GAROFALO, J ;
SCHEIDT, WR .
INORGANIC & NUCLEAR CHEMISTRY LETTERS, 1975, 11 (02) :107-112
[9]   A SEMI-EMPIRICAL METHOD OF ABSORPTION CORRECTION [J].
NORTH, ACT ;
PHILLIPS, DC ;
MATHEWS, FS .
ACTA CRYSTALLOGRAPHICA SECTION A-CRYSTAL PHYSICS DIFFRACTION THEORETICAL AND GENERAL CRYSTALLOGRAPHY, 1968, A 24 :351-&
[10]  
OCHSENBEIN P, 1994, ANGEW CHEM INT EDIT, V33, P348, DOI 10.1002/anie.199403481