SOLUTION CONFORMATIONS OF DODECASUBSTITUTED COBALT(II) PORPHYRINS

被引:35
作者
MEDFORTH, CJ
HOBBS, JD
RODRIGUEZ, MR
ABRAHAM, RJ
SMITH, KM
SHELNUTT, JA
机构
[1] SANDIA NATL LABS, DEPT FUEL SCI, ALBUQUERQUE, NM 87185 USA
[2] UNIV LIVERPOOL, DEPT CHEM, LIVERPOOL L69 3BX, MERSEYSIDE, ENGLAND
关键词
D O I
10.1021/ic00110a008
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The solution conformations of seven dodecasubstituted porphyrins, which generally show extremely nonplanar structures in the crystalline state, have been investigated using a method that combines proton NMR spectroscopy and molecular mechanics calculations. By comparison of the proton paramagnetic shifts measured for cobalt(II) complexes of these porphyrins with the dipolar shifts calculated using geometric factors obtained either from crystallographic data or from molecular mechanics structures, it is determined that the conformations of the macrocycles and their substituents are similar in solution and in the crystalline state. Thus, the nonplanar cobalt(II) porphyrins that have well-defined cavity structures in the crystalline state retain these cavities in solution. Variable-temperature proton NMR spectroscopy is used to estimate the dynamic stabilities of the cavity structures. The porphyrins with cavities are found to behave differently from planar porphyrins without cavities with regard to the formation of pi-complexes with 1,3,5-trinitrobenzene. It is suggested that the cavities may modulate a range of porphyrin-substrate interactions, potentially making these porphyrins useful as regio- and stereoselective oxidation catalysts and in the preparation of complexes with well-defined ligand orientations.
引用
收藏
页码:1333 / 1341
页数:9
相关论文
共 81 条
[1]   RESONANCE RAMAN-SPECTRA OF OCTAETHYLPORPHYRINATO-NI(II) AND MESO-DEUTERATED AND N-15 SUBSTITUTED DERIVATIVES .2. NORMAL COORDINATE ANALYSIS [J].
ABE, M ;
KITAGAWA, T ;
KYOGOKU, Y .
JOURNAL OF CHEMICAL PHYSICS, 1978, 69 (10) :4526-4534
[2]  
Abraham R.J., 1988, INTRO NMR SPECTROSCO
[3]   NMR-SPECTRA OF THE PORPHYRINS .39. PARAMAGNETIC SHIFTS IN COBALT(II) PORPHYRINS [J].
ABRAHAM, RJ ;
MARSDEN, I ;
XIUJING, L .
MAGNETIC RESONANCE IN CHEMISTRY, 1990, 28 (12) :1051-1057
[4]   PLANAR NONPLANAR CONFORMATIONAL EQUILIBRIUM IN METAL DERIVATIVES OF OCTAETHYLPORPHYRIN AND MESO-NITROOCTAETHYLPORPHYRIN [J].
ANDERSON, KK ;
HOBBS, JD ;
LUO, LA ;
STANLEY, KD ;
QUIRKE, JME ;
SHELNUTT, JA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (26) :12346-12352
[5]   CRYSTALLOGRAPHIC AND EXAFS STUDIES OF CONFORMATIONALLY DESIGNED NONPLANAR NICKEL(II) PORPHYRINS [J].
BARKIGIA, KM ;
RENNER, MW ;
FURENLID, LR ;
MEDFORTH, CJ ;
SMITH, KM ;
FAJER, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (09) :3627-3635
[6]   STRUCTURAL AND THEORETICAL-MODELS OF PHOTOSYNTHETIC CHROMOPHORES - IMPLICATIONS FOR REDOX, LIGHT-ABSORPTION PROPERTIES AND VECTORIAL ELECTRON FLOW [J].
BARKIGIA, KM ;
CHANTRANUPONG, L ;
SMITH, KM ;
FAJER, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (22) :7566-7567
[7]   NONPLANAR PORPHYRINS - X-RAY STRUCTURES OF (2,3,7,8,12,13,17,18-OCTAETHYL-5,10,15,20-TETRAPHENYLPOPHINATO)ZINC(II) AND (2,3,7,8,12,13,17,18-OCTAMETHYL-5,10,15,20-TETRAPHENYLPORPHINATO)ZINC(II) [J].
BARKIGIA, KM ;
BERBER, MD ;
FAJER, J ;
MEDFORTH, CJ ;
RENNER, MW ;
SMITH, KM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (24) :8851-8857
[8]  
BARKIGIA KM, COMMUNICATION
[9]   MAGNETIC-RESONANCE STUDY OF METAL-PORPHYRIN-CAFFEINE COMPLEXES [J].
BARRY, CD ;
HILL, HAO ;
SADLER, PJ ;
WILLIAMS, RJP .
PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL PHYSICAL AND ENGINEERING SCIENCES, 1973, 334 (1599) :493-504
[10]   MOLECULAR-STRUCTURES OF PORPHYRIN COMPLEXES IN SOLUTION - H-1 NUCLEAR MAGNETIC-RESONANCE SPECTROSCOPIC INVESTIGATION OF INTERACTION BETWEEN 2,4,7-TRINITROFLUORENONE AND NICKEL (II) AND COBALT(II) MESOPORPHYRIN IX DIMETHYL ESTERS [J].
BARRY, CD ;
HILL, HAO ;
MANN, BE ;
SADLER, PJ ;
WILLIAMS, RJP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (14) :4545-4551