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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Steric control over the formation of cis and trans bis-chelated palladium(II) complexes using a new series of flexible N,P pyridyl-phosphine ligands
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Steric control over the formation of cis and trans bis-chelated palladium(II) complexes using a new series of flexible N,P pyridyl-phosphine ligands

机译：使用一系列新的柔性N，P吡啶基膦配体对立体式控制顺式和反式双螯合钯（II）配合物的形成

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摘要

The deprotection of phosphonium chloride salts [PR2(CH2OH)2]+Cl- and subsequent condensation reaction with N-methyl-2-aminopyridine has been carried out to give a series of ligands of the form PR2CH2N(CH3)C5H4N (R = Ph 6, Cy 7, t-Bu 8) which have been fully characterised either as the pure ligand (6) or the air stable borane adducts (R = Cy 7a, t-Bu 8a). The 1 : 1 reactions of 6, 7 and 8 with PdCl2(COD) gave the N,P chelate complexes [Pd{PR2CH2N(CH3)C5H4N}Cl2]; the Cy (10) and t-Bu (11) complexes were characterised by X-ray crystallography. The bisligated species [Pd{PCy2CH2N(CH3)C5H4N}2Cl2] (12) was obtained when the reaction was carried out at higher temperatures and the ligands were found to be coordinated to the metal in a trans configuration through the phosphorus donors. Abstraction of the chlorides from the bis-ligated species 12, using silver salts, resulted in the coordination of the pyridine ring forming the bis-chelate complex [Pd{PCy2CH2N(CH3)C5H4N}2]~(2+) 13. In comparison, the palladium bis-chelate complex of ligand 5 [Pd{PPh2CH2N(CH3)C5H4N}2]~(2+) (14) was shown to form in a cis configuration and was fully characterised by X-ray crystallography.
机译：进行了氯化phospho盐[PR2（CH2OH）2] + Cl-的脱保护和随后与N-甲基-2-氨基吡啶的缩合反应，得到了一系列PR2CH2N（CH3）C5H4N形式的配体（R = Ph 6，Cy 7，t-Bu 8）已完全表征为纯配体（6）或空气稳定的硼烷加合物（R = Cy 7a，t-Bu 8a）。 6、7和8与PdCl2（COD）的1：1反应得到N，P螯合物[Pd {PR2CH2N（CH3）C5H4N} Cl2]; Cy（10）和t-Bu（11）配合物通过X射线晶体学表征。当在较高温度下进行反应，发现配体与金属配位时，通过磷供体以反式配位得到了双连接的[Pd {PCy2CH2N（CH3）C5H4N} 2Cl2]（12）。使用银盐从双连接的物种12中提取氯化物，导致吡啶环配位形成双螯合物[Pd {PCy2CH2N（CH3）C5H4N} 2]〜（2+）13。 ，配体5 [Pd {PPh2CH2N（CH3）C5H4N} 2]〜（2+）（14）的钯双螯合物显示出顺式构型，并通过X射线晶体学对其进行了充分表征。

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