Exploring the coordination chemistry and reactivity of dialkylamino- and bis(dialkylamino)-phosphines in the coordination sphere of metals
摘要：
The coordination chemistry of a range of dialkylamino- and bisdialkylamino-phosphines, RxPNR′23 −xx1 or 2; R Cl, Me, Ph, C6F5; R′ Et, Pri,1–7, has been studied and the resulting Group 6 tetracarbonyl and platinum dichloride bisphosphine complexes fully characterised. Subsequently, the reactivity of the P–N bonds of the metal-bound phosphines was probed. Treatment of R″OH R″ Me, Et, allyl solutions of the bisdialkylaminodiphenylphosphine complexes with anhydrous HCl gas led to substitution of NR′2by OR″; the resulting P-alkoxy complexes were isolated in excellent yields. Acidification of ethylene glycol solutions of the aminophosphine complexes afforded the corresponding bischlorodiphenylphosphine derivatives. Following reaction oftrans-WCO4PNEt2Ph22with either aqueous HCl or H2SO4,trans-WCO4POHPh22could be isolated as its dichloromethane solvate in excellent yield 81. Reactions of the bisbisdialkylaminophenylphosphine complexes under identical conditions yielded a range of unidentified products. Reactions of ligands1–7with RhClCO22and elemental selenium have been undertaken and the products used to assess the phosphines' donor capabilities. Depending on the substituents at phosphorus, eithertrans-diphosphine orcis-dicarbonyl complexes result from reaction with RhClCO22. The sterically demanding phosphine PNPri22Ph5proved unreactive towards complexation with metals, although its selenide could be prepared and isolated. In order to probe the observed lack of oxidation or complexation the molecular structure PNPri22C6F5has been determined by X-ray crystallography.
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关键词：
polyphosphines complexes tridentate phosphines tetradentate phosphines nitrogen-containing phosphines sulfur-containing phosphines ferrocenyl phosphines Group 6 to 10 transition metals crystal structures
DOI：
10.1039/b208886j
被引量：
年份：
2003
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