AN NMR INVESTIGATION OF 1,2-METALLOTROPIC SHIFTS IN TRANSITION-METAL COMPLEXES OF BENZO[C]CINNOLINE AND PYRIDAZINES

被引：16

作者：

ABEL, EW ^{[1
]}

BLACKWALL, ES ^{[1
]}

ORRELL, KG ^{[1
]}

SIK, V ^{[1
]}

机构：

[1] UNIV EXETER,DEPT CHEM,EXETER EX4 4QD,DEVON,ENGLAND

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1994年 / 464卷 / 02期

关键词：

TUNGSTEN; RHODIUM; PYRIDAZINE; NUCLEAR MAGNETIC RESONANCE; METALLOTROPIC SHIFT;

D O I：

10.1016/0022-328X(94)87270-8

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Complexes of types [W(CO)(5)L], [cis-Rh(CO)(2)C1L] (L = benzo[c]cinnoline) and [W(CO)(5)L'] (L' = pyridazine, 3-methylpyridazine, and 4-methylpyridazine) have been synthesized and shown to exhibit, in organic solvents, intramolecular metal-nitrogen 1,2-fluxional shifts, which have been quantitatively studied by ID bandshape analysis and 2D-EXSY NMR experiments. Energy barriers for the metallotropic shifts in the pyridazine complexes are ca. 20 kJ mol(-1) higher than in the benzo[c]cinnoline complexes. These differences are discussed in terms of the ground state and likely transition state species for this fluxional process.

引用

页码：163 / 170

页数：8

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