Preparation and properties of rhodium(I) and iridium(I) diolefin complexes of heterodifunctional phosphorus–imine chelating ligands and a related iminophosphine. 103Rh NMR parameters of the rhodium complexes obtained via indirect two-dimensional 31P, 103Rh{1H} NMR spectroscopy

Autor: David J. Law, Ronald G. Cavell, Glen Bigam
Rok vydání: 1995
Předmět:
Zdroj: Canadian Journal of Chemistry. 73:635-642
ISSN: 1480-3291
0008-4042
DOI: 10.1139/v95-082
Popis: Treatment of [M(cod)Cl]2 (M = Rh, Ir) with iminophosphoranophosphine ligands of the type Ph2PQP(Ph2)=NSiMe3 (Q = CH2, CH2CH2, 1,2-C6H4) afforded the new metallacycles [Formula: see text] through elimination of Me3SiCl, ultimately "anchoring" the ligand to the metal through a metal–nitrogen σ bond. The phosphine functionality completes the chelate. Cationic complexes of the type [M(cod)L2]+PF6− (M = Rh or Ir; L2 = Ph2PQPPh2NR where Q = CH2, CH(CH3), 1,2-C6H4, and R = p-C6F4CN, C6H2F(NO2)2, and C6H3(NO2)2 or L = Ph2PN=C(H)Ph) were readily prepared by treating [M(cod)Cl]2 with L2 and KPF6. The detection and chemical shift determination of the insensitive 103Rh nucleus was easily accomplished via 31P detected indirect two-dimensional 31P, 103Rh{1H} NMR spectroscopy. The 103Rh, 1H, and 31P NMR data are discussed. Keywords: rhodium, iridium, phosphoranimine, iminophosphine, Rh NMR.
Databáze: OpenAIRE