Synthesis and characterization of palladium(II) complexes with a novel chelating iminocarbene ligand

被引:53
作者
Froseth, M [1 ]
Dhindsa, A [1 ]
Roise, H [1 ]
Tilset, M [1 ]
机构
[1] Univ Oslo, Dept Chem, N-0315 Oslo, Norway
关键词
D O I
10.1039/b308275j
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction between 1-chloro-2-(2,6-diisopropylphenylimino) propane and N-methylimidazole yields 3-methyl-1{ 2-(2,6-diisopropylphenylimino) propyl} imidazolium] chloride, (C-N) . HCl (2). A silver(I) iminocarbene complex formulated as (C-N)(2)Ag+ AgCl2- is formed in the reaction between 2 and Ag2O. Carbene transfer to Pd occurs when 2 is treated with (COD) Pd(Cl)(X) to yield (C - N) Pd(Cl)(X) (4a, X = Cl; 4b, X = CH3). Chloride abstraction from 4a and 4b with AgPF6 in MeCN yields (C - N) Pd(NCMe)(X) +PF6- (5a and 5b). A second chloride abstraction can be done with 5a to yield (C - N) Pd(NCMe)(2)(2+) (PF6-)(2) (6). An X-ray structure determination of 4a verifies the chelating nature of the iminocarbene ligand system and shows that the molecule adopts a boat conformation with Pd and the CH2 link between the carbene and the imine occupying the two apical positions. The species 4 - 6 have been subjected to extensive analysis by variable-temperature, EXSY, and NOESY NMR spectroscopy in various solvents. In the weakly coordinating solvent nitromethane, 4a and 4b exist as square planar species in which the iminocarbene acts as a C, N-chelating ligand. NMR experiments reveal a dynamic behavior of 4a that involves a boat "flip". This process is fast even at - 40 degreesC for 4b but considerably slower for 4a. In more coordinating solvents, evidence is seen for solvent-dependent equilibra that involve rapid interconversion between the chelating kappa(2)(C, N) structures (kappa(2)-(C - N)) Pd(Cl)(X) and non-chelating kappa(1)(C) iminocarbene structures (kappa(1)-(C - N)) Pd(Cl)(X)(Solvent). Complex 5a exists as two interconverting species, possibly cis/trans isomers by interchange of the MeCN and Cl ligands, whereas no evidence for dynamic processes is seen for 5b and 6.
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页码:4516 / 4524
页数:9
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