We present a free web application for the calculation of the buried volume (% VBur) of NHC ligands. The web application provides a graphic and user-friendly interface to the SambVca program, developed for the calculation of % VBur values not only of NHC ligands but also of other classic organometallic ligands such as, for example, phosphanes and cyclopentadienyl-based ligands. To provide a reliable procedure for the calculation of % VBur values we tested our approach in the interpretation of the binding energies of NHC ligands in Cp*Ru(NHC)Cl complexes in terms of steric and electronic parameters.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

SambVca: A Web Application for the Calculation of the Buried Volume of N‐Heterocyclic Carbene Ligands

Palladium catalysed allylic substitution has emerged as one of the more useful synthetic methods for the construction of C-C and C-X bonds. The reaction offers the advantages of mild reaction conditions, as well as the ability to accomodate a wide range of nucleophiles and their electrophilic partners. The issues of regiocontrol, diastereocontrol and enantiocontrol have been documented by a number of researchers over the last twenty years. The levels of selectivity in many cases are very high, and current research is driving these selectivities higher still. A greater understanding of the nature of the process is occurring as more detailed mechanistic and structural studies are being undertaken. Many uses have been found for palladium catalysed allylic substitution methodology, since the strong stereocontrol allows for the selective formation of numerous products. A few other metals are also able to catalyse allylic substitution, with modified stereochemical behaviour, although these are currently less well documented than for palladium catalysed process.

Selectivity in palladium catalysed allylic substitution

INTRODUCTION Recent Advances in C-P Bond Formation Nomenclature of C-P Compounds Information Sources for C-P Compounds SYNTHESIS OF ORGANOPHOSPHORUS COMPOUNDS FROM ELEMENTAL PHOSPHORUS Introduction Availability of Elemental Phosphorus Attack on Elemental Phosphorus by Nucleophiles Radical Attack on Elemental Phosphorus Direct Addition to P-Systems Oxidative Additions with Olefins Experimental Procedures Summary References C-P BOND FORMATION USING NUCLEOPHILIC TRIVALENT PHOSPHORUS REAGENTS Introduction Substitution Reactions Using Neutral Trivalent Phosphorus Reagents Substitution Reactions Using Anionic Trivalent Phosphorus Reagents Preparations Of A-substituted Phosphoryl Compounds Conjugate Addition Reactions Experimental Procedures References C-P BOND FORMATION VIA DISPLACEMENT, ADDITION, OR REARRANGEMENT Introduction Phosphorus-halogen Compounds Substitution Reactions on Phosphorus-halogen Compounds Using Organometallics and Related Reagents Addition Reactions of P-H Compounds Addition Reactions of P-Cl Compounds Rearrangements Resulting In The Formation Of New P-C Bonds Experimental Procedures References PENTACOORDINATE PHOSPHORUS Introduction General Structure of Pentacoordinate Phosphorus Stable Phosphoranes Carbonnphosphorus Bond Formation Involving Phosphorane Intermediates Experimental Procedures References AROMATIC AND VINYLIC C-P BONDS Introduction Aromatic Carbon-Phosphorus Bond Formation Vinylic Carbon-Phosphorus Bond Formation Experimental Procedures References Index

http://chemistry-chemists.com/chemister/Praktikum/synthesis-of-carbon-phosphorus-bonds-2004.pdf

Laurie E. McKinney

Papers

A Fourier transform carbon-13 NMR study of the electronic effects of phosphorus, arsenic, and antimony ligands in transition-metal carbonyl complexes

A Fourier transform carbon-13 NMR study of the electronic effects of phosphorus, arsenic, and antimony ligands in transition-metal carbonyl complexes