NUCLEAR MAGNETIC-RESONANCE STUDY OF METAL-COMPLEXES .2. CONFORMATIONS OF 1,2-DIAMINE CHELATE RINGS WITH C-PHENYL GROUP(S) IN COBALT(III) AND PLATINUM(II) COMPLEXES

被引:37
作者
YANO, S [1 ]
TUKADA, T [1 ]
SABURI, M [1 ]
YOSHIKAWA, S [1 ]
机构
[1] UNIV TOKYO,FAC ENGN,DEPT SYNTHET CHEM,BUNKYO KU,TOKYO 113,JAPAN
关键词
D O I
10.1021/ic50187a037
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The proton magnetic resonance spectra of [Co(CN)4(R-phenen)]-(R-phenen=(R)-phenylethylenediamine), [Pt-(NH3)2(pn-d1)]2+ (pn-d1,=2-deuterio-1, 2-diaminopropane), [Pt (5-pn-d2)2]2+ (S-pn-d2=(25)-l,l-dideuterio-l,2-di-aminopropane), [[Pt (5-pn-d2)2]2+(5,5-bn = (25,35)-2,3butanediamine), and [Pt (en)((-)D-stien)]2+ ((-)D-stien=stil benediamine) have been measured. The 13C NMR spectra of these Pt(II) complexes and [Pt(en)(R-phenen)]2+ have been obtained. Values of JH-c-c-H indicate a strong preference for the equatorial orientation of C-C6H5 in (R)-phenylethylenediamine of Co(III) complexes. For Pt(II) complexes, values of Jpt,-N-C-H and Jpt-N-C-C suggest that 1,2-diaminopropane (propylenediamine) and (R)-phenylethylenediamine chelate rings have unsymmetrical gauche conformations and (2S,3S)-2,3-butanediamine and (-)D-stilbenediamine chelate rings take symmetrical gauche conformations, while meso-stilbenediamine chelate changes its conformation rapidly fromλto δ and vice versa rapidly on the NMR time scale. For the diamine chelates with C-phenyl group(s) a Karplus-like dihedral angle dependence for the Jpt-N-C-C*, where C* is a phenyl carbon atom which attaches on the membered-carbon atom, was observed. These 3Jpt-C* values were very similar to those for the Jpt-N-C-C-CH3 in the diamine chelates with C-methyl group(s). © 1978, American Chemical Society. All rights reserved.
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页码:2520 / 2526
页数:7
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