Phosphinines coordination chemistry

Me zaillies, Nicolas, Mathey, Francois, and I e Floch, Pascal, The Coordination Chemistry of Phosphinines Their Polydentate and Macrocyclic... 

Phosphinines are a special group of phosphaaUcenes in which the P=C double bond becomes integrated into the aromatic system of benzene and related arenes. The majority of examples are based on the mono-phospha-benzenes, but di-and triphospha-benzenes in various substitution patterns have also been employed as ligands. The coordination chemistry of this class of ligands has been reviewed. ... 

The coordination chemistry of phosphinines, including their polydentate and macrocyclic derivatives, has been reviewed. Valence isomerism of phosphinines has continued to attract attention. The structures, energetics, and vibrational spectra of valence isomers of the parent system, phosphinine, (CH)sP, have been studied by theoretical techniques. Phosphatriafulvenes (390) readily react with kinetically-stabilised phosphaalkynes to give, initially, 1,3-diphos-phinines, e.g., (391), which then undergo valence isomerism on heating in toluene... 

Abstract Recent developments in the chemistry of phosphinines are reported. This chapter presents and discusses the most important breakthroughs achieved during the last decade. New synthetic approaches allowing the synthesis of polyfunctional phosphinines as well as improvements of well known methods are reported. The use of phosphinines in coordination chemistry is also presented with particular emphasis on their use in the stabilization of low valent and highly reduced transition metal complexes. Another aim of this review is to discuss recent applications of phosphinines, and structures derived directly from phosphinines such as phosphacyclohexadienyl anions and phosphabarrelenes, as ligands in homogeneous catalysis. 

Meyer, T. J., Oxidation-Reduction and Related Reactions of Metal-Metal Bonds Mezaillies, Nicolas, Mathey, Erancois, and Ee Eloch, Pascal, The Coordination Chemistry of Phosphinines Their Polydentate and Macrocyclic Derivatives Michel, Sarah L. J., Hoffman, Brian M., Baum, Sven M., and Barrett, Anthony G. M., Peripherally Functionalized Porphyrazines Novel Metallo-... 

The chemistry of phosphinines syntheses, coordination chemistry, and catalysis 06COC3. 

Relatively little has appeared in the past year on the synthesis and reactivity of the six membered, potentially aromatic, phosphinine ring system. A route to the first C2-asymmetric phosphinine (147), derived from (+ )-camphor, has been developed from the reaction of a pyrylium salt precursor with P(TMS)3. The chiral phosphinine is a crystalline, air-stable solid and forms complexes with metal ions, therefore having some potential as a ligand in homogeneous eatalysis." A pyrylium salt-P(TMS)3 final step was also used in the synthesis of a series of 2-(2 -halo)triarylphosphinines (148), subsequently shown to form a series of tungsten(0) and rhodium(I) complexes involving coordination of the phosphorus sp lone pair to the metal." Interest has continued in studies of the coordination chemistry of phosphabarrelenes, derived from the established reactions of phosphinines... 

Developments in the coordination chemistry of phosphinines 13EJI187. Developing iron and ruthenimn complexes for potential nonlinear optical appbcations 13CCR1438. 

N. MezaUles, F. Mathey, and P. LeFloch, The coordination chemistry of phosphinines. Prog. Inorg. Chem., 49,453, 2001. 

Interest in the chemistry of the 6ji-phosphinine (phosphabenzene) system has continued, although considerably fewer papers have appeared compared to recent years. The synthesis, coordination chemistry and catalytic applications of phosphi-nines have been reviewed." New chiral bidentate phosphinine ligands (220) have been prepared and their coordination chemistry and applications in rhodium-catalysed asymmetric hydrogenations assessed." The diphosphinine (221) continues to find new applications as a ligand in homogeneous catalysis" and a new mode of coordination to a metal has been identified for the phosphinine (222), two such ligands simultaneously bridging a Mn-Mn bond." ... 

Mezailles N, Mathey F, Le Floch P (2001) The coordination chemistry of phosphinines, their polydentate and macrocyclic derivatives. Prog Inorg Chem 49 455... 

Blug M (2009) Phosphinines as precursors for phosphinine anions and phosphabarrelenes coordination chemistry, catalysis and stabilisation of nanoparticles. PhD Thesis, Ecole... 

Markl G (1990) Phosphinines. In Regitz M, Scherer OJ (eds) Multiple bonds and low coordination in phosphorus chemistry. Georg Thieme Verlag, Stuttgart, p 220, and references cited therein... 

The aromaticity of the six-membered ring phosphinine is similar to that of benzene (different aromaticity measures all exhibit about 90% of the benzene values), as reviewed previously [4, 278]. These characteristics reflect in the frequently used term phosphabenzene (for a recent review on its chemistry, coordination, and catalytic behavior see [279]). The numerical values for some aromaticity indicators... 

Phosphabenzenes (sA, -phosphinines) have been known for a long time and played a major role in the development of the chemistry of low-coordinated phosphorus [34]. In contrast, all previous attempts to prepare their valency isomers, which also include the cage-like phosphaprismanes and phosphabenzvalenes, failed. Success was first possible after the development of syntheses for cyclobutadienes on the one hand, and for phosphaalkynes on the other. 

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