EVIDENCE OF STERIC INFLUENCES ON THE CO-C BOND LENGTHS IN VITAMIN-B12 MODEL COMPOUNDS .2. CRYSTAL-STRUCTURES OF 2 ADAMANTYLCOBALOXIMES WITH THE NEUTRAL LIGANDS H2O AND PPH2ET

被引：15

作者：

GEREMIA, S

RANDACCIO, L

ZANGRANDO, E

ANTOLINI, L

机构：

[1] UNIV TRIESTE,DIPARTIMENTO SCI CHIM,I-34127 TRIESTE,ITALY

[2] UNIV MODENA,DIPARTIMENTO CHIM,I-41100 MODENA,ITALY

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1992年 / 425卷 / 1-2期

关键词：

D O I：

10.1016/0022-328X(92)80029-W

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The structures of trans-Co(DH)2adam(H2O) (1) and trans-Co(D)(DH2)adam(PPh2Et) (2), where D = dianion of dimethylglyoxime, and adam = adamantyl group, are determined by X-ray crystal structure analysis. The Co-C bond lengths are 2.129(3) angstrom (1) and 2.217(7) angstrom (2). The alpha and d (measures of the geometrical deformation of the equatorial moiety) are -15.8-degrees and -0.093 angstrom in 1 and -3.2-degrees and -0.011 angstrom in 2, respectively. These differences are ascribed to steric influences of the neutral ligand. Linear regression analyses of Co-C bond lengths with alpha and d in adamantylcobaloximes have confirmed that the axial-equatorial interactions are of considerable importance in these systems. The comparison between adamantyl- and methyl-cobaloximes suggests a higher elasticity of the Co-C(adam) bond compared to Co-C(Me).

引用

页码：131 / 139

页数：9

共 17 条

[1] CAMBRIDGE CRYSTALLOGRAPHIC DATA CENTER - COMPUTER-BASED SEARCH, RETRIEVAL, ANALYSIS AND DISPLAY OF INFORMATION [J].

ALLEN, FH ;

BELLARD, S ;

BRICE, MD ;

CARTWRIGHT, BA ;

DOUBLEDAY, A ;

HIGGS, H ;

HUMMELINK, T ;

HUMMELINKPETERS, BG ;

KENNARD, O ;

MOTHERWELL, WDS ;

RODGERS, JR ;

WATSON, DG .

ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 1979, 35 (OCT) :2331-2339

[2]

ATTIA MW, 1987, ACTA CRYSTALLOGR C, V43, P1521

[3]

FRENZ BA, 1980, ENRAF NONIUS STRUCTU

[4]

GEREMIA, 1991, J ORGANOMET CHEM, V408, P95

[5] MECHANISMS OF COENZYME-B12 - DEPENDENT REARRANGEMENTS [J].

HALPERN, J .

SCIENCE, 1985, 227 (4689) :869-875

[6]

HEY BP, 1987, J AM CHEM SOC, V109, P8012

[7]

JOHNSON CK, 1965, ORNL3794 REP

[8] TRANSFER TO ORGANOMETALLIC CHEMISTRY OF SUBSTITUENT CONSTANTS FROM ORGANIC-CHEMISTRY .1. RESOLUTION OF LONGSTANDING ANOMALIES IN THE CHEMISTRY OF ORGANOCOBALT-B12 MODELS AND ORGANOCOBALAMINS [J].

MARZILLI, LG ;

BAYO, F ;

SUMMERS, MF ;

THOMAS, LB ;

ZANGRANDO, E ;

BRESCIANIPAHOR, N ;

MARI, M ;

RANDACCIO, L .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (20) :6045-6052

[9] DECOMPOSITION OF (ALPHA-PHENETHYL)BIS(DIMETHYLGLYOXIMATO)COBALT(III) COMPLEXES - INFLUENCE OF ELECTRONIC AND STERIC FACTORS ON THE KINETICS AND THERMODYNAMICS OF COBALT CARBON BOND-DISSOCIATION [J].

NG, FTT ;

REMPEL, GL ;

MANCUSO, C ;

HALPERN, J .

ORGANOMETALLICS, 1990, 9 (10) :2762-2772

[10]

Pahor N. B., 1985, COORDIN CHEM REV, V63, P1

← 1 2 →