BETA-HALOGENATED-PYRROLE PORPHYRINS - MOLECULAR-STRUCTURES OF 2,3,7,8,12,13,17,18-OCTABROMO-5,10,15,20-TETRAMESITYLPORPHYRIN, NICKEL(II) 2,3,7,8,12,13,17,18-OCTABROMO-5,10,15,20-TETRAMESITYLPORPHYRIN, AND NICKEL(II) 2,3,7,8,12,13,17,18-OCTABROMO-5,10,15,20-TETRAKIS(PENTAFLUOROPHENYL)PORPHYRIN

被引:188
作者
MANDON, D
OCHSENBEIN, P
FISCHER, J
WEISS, R
JAYARAJ, K
AUSTIN, RN
GOLD, A
WHITE, PS
BRIGAUD, O
BATTIONI, P
MANSUY, D
机构
[1] UNIV STRASBOURG 1,INST LE BEL,CRISTALLOCHIM & CHIM STRUCT LAB,UA 424,4 RUE BLAISE PASCAL,F-67070 STRASBOURG,FRANCE
[2] UNIV N CAROLINA,DEPT CHEM,CHAPEL HILL,NC 27599
[3] UNIV N CAROLINA,DEPT ENVIRONM SCI & ENGN,CHAPEL HILL,NC 27599
[4] UNIV PARIS 05,CHIM & BIOCHIM PHARMACOL LAB,F-75270 PARIS 06,FRANCE
关键词
D O I
10.1021/ic00037a012
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The X-ray structures of the beta-substituted-pyrrole tetraarylporphyrin 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetramesitylporphyrin (H2TMOBP), its nickel(II) complex (NiTMOBP), and the nickel(II) derivative of 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (NiTPFPOBP.1/2CH2Cl2) are reported. The synthesis of the free base H2TPFPOBP is also described. All these molecules are nonplanar, displaying saddle-shaped conformations. The saddle distortions minimize the intramolecular steric interactions between the bromine substituents and the ortho') carbon atoms or ortho (ortho') substituents of the phenyl rings, and consequently, the corresponding contact distances have similar values in all compounds. Because of the distortion of the porphyrin cores, the cavity defined by the ortho (ortho') substituents gives slightly less steric protection than in the nonbrominated nearly planar ortho- and ortho'-substituted tetraarylporphyrin complexes. Crystallographic data: C56H46N4Br8 (H2TMOBP), tetragonal, space group P42(1)cBAR, a = b = 15.085 (4) angstrom, c = 14.056 (4) angstrom, V = 3198.8 angstrom 3, Z = 2, R(F) = 0.054, R(wF) = 0.069 based on 638 reflections with I(o) > 3-sigma(I(o)), T = 298 K; NiC56H44N4Br8.18 (NiTMOBP), tetragonal, space group P42(1)cBAR, a = b = 15.024 (3) angstrom, c = 14.068 (6) angstrom, V = 3175.2 angstrom 3, Z = 2, R(F) = 0.049, R(wF) = 0.057 based on 877 reflections with I(o) > 2.5-sigma(I(o)), T = 298 K; NiC44N4F20Br8.1/2CH2Cl2 (NiTPFPOBP.1/2CH2Cl2), monoclinic, space group C2/c, a = 18.105 (3) angstrom, b = 22.141 (5) angstrom, c = 24.301 (5) angstrom, beta = 93.32 (2)-degrees, V = 9725.5 angstrom 3, Z = 8, R(F) = 0.047, R(wF) = 0.064 based on 2896 reflections with I(o) > 3-sigma(I(o)), T = 298 K.
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页码:2044 / 2049
页数:6
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