Formation of novel P-functionalised ligands by insertion of CyNC into the ZrP bonds of [Cp° 2ZrCl(PHCy)] (Cp°=η 5-C 5EtMe 4, Cy=cyclohexyl) and [Cp′ 2ZrCl(PHTipp)] (Cp′=η 5-C 5H 4Me, Tipp=2,4,6-Pr i3C 6H 2). Molecular structures of [Cp° 2ZrCl{η 2-NCyC(PHCy)}] and [Cp′ 2Zr(Cl){η 2-NCyC(PHTipp)}

Abstract

[Cp′ 2ZrCl(PHTipp)] ( 1) (Cp′=η 5-C 5H 4Me, Tipp=2,4,6-Pr i 3C 6H 2) and [Cp° 2ZrCl(PHCy)] ( 2) (Cp°=η 5-C 5EtMe 4, Cy=cyclohexyl) readily insert CyNC to give [Cp′ 2ZrCl{η 2-NCyC(PHTipp)}] ( 3) and [Cp° 2ZrCl{η 2-NCyC(PHCy)}] ( 4). 3 and 4 were characterised spectroscopically (IR, NMR, MS) and by crystal structure determination, which showed an η 2 bonding mode (C,N) of the NCyC(PHR) ligands. Of the two possible coordination modes of the ligand, 3 is obtained exclusively as the exo isomer, in which the NCy group is adjacent to the ZrCl bond, while for 4, both isomers ( exo and endo) are formed [1:1.5 ( 4a: 4b)], whereby the endo isomer is favoured. The exo isomer 4a was structurally characterised.