New N-pyrazole, P-phosphinite hybrid ligands and corresponding Rh(I) complexes: X-ray crystal structures of complexes with [Rh, N, P-phosphinite, Cl, (CO)] core

Two new N-pyrazole, P-phosphinite hybrid ligands 3-(3,5-dimethyl-1H-pyrazol-1-yl)propyldiphenylphosphinite (L3) and 2-(3,5-diphenyl-1H-pyrazol-1-yl)ethyldiphenylphosphinite (L4) are presented. The reactivity of these ligands and two other ligands reported in the literature (3,5-dimethyl-1H-pyrazol-1-yl)methyldiphenylphosphinite (L1) and 2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyldiphenylphosphinite (L2) towards [RhCl(CO)2]2 (1) have been studied and complexes [RhCl(CO)L] (L = L2 (2), L3 (3) and L4 (4)) have been obtained. For L1 only decomposition products have been achieved. All complexes were fully characterised by analytical and spectroscopic methods and the resolution of the crystalline structure of complexes 2 and 3 by single-crystal X-ray diffraction are also presented. In these complexes, the ligands are coordinated via κ2(N,P) to Rh(I), forming metallocycles of seven (2 and 4) or eight (3) members and finish its coordination with a carbonyl monoxide and a trans-chlorine to phosphorus atom. In both complexes, weak intermolecular interactions are present. NMR studies of complexes 2–4 show the chain N–(CH2)x–O becomes rigid and the protons diastereotopic.