6533b7d1fe1ef96bd125d509
RESEARCH PRODUCT
Tantalocenehydridephosphorus chemistry.
Gilles BoniPhilippe SauvageotClaude MoïseOlivier BlacqueNicolas PoujaudMarek M. Kubickisubject
ChemistryPhosphideStereochemistryLigandRegioselectivityElectron donorCrystal structureInorganic ChemistryCrystallographychemistry.chemical_compoundCyclopentadienyl complexMaterials ChemistryPhosphoniumPhysical and Theoretical ChemistryLone pairdescription
Abstract The aim of this paper is to look for a better knowledge of the behaviour of bent tantalocenes that bear hydrides, phosphorus PR2X (R=Me, Ph; X=H, lone pair) and cyclopentadienyl (Cp=C5H5, Cp′=C5H2tBu(Me)2, Cp*=C5Me5) ligands. An orbital control of regioselectivity of insertion of the PR2 phosphide fragment of chlorophosphines PR2Cl into the central TaH bond of trihydrides Cp2TaH3 leading to the formation of metallophosphonium cations is discussed. Neutralisation of cationic complexes with strong bases leads either to the Ta(V)–phosphide or to the Ta(III)–phosphine species depending on the nature of the cyclopentadienyl ligand; good electron donor Cp′ and Cp* rings favour the formation of Ta(V)–phosphide species, while C5H5 orients neutralisation towards Ta(III)–phosphine ones. These trends are roughly confirmed by DFT calculations. The X-ray structure of the first tantalocene phosphonium ionic compound [CpCp′TaH2(PMe2H)]PF6 (Cp′=C5H2tBu(Me)2) as well as that of the bimetallic complex Cp2Ta(H)(μ-PPh2,H)Fe(CO)3 are also reported.
year | journal | country | edition | language |
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2002-03-01 | Polyhedron |