225653-18-9

Upstream product

• 6737-42-4 1,3-bis-(diphenylphosphino)propane 
• 484-11-7 2.9-dimethyl-1,10-phenanthroline 

Relevant academic research and scientific papers

Solid-state and solution structural properties of copper(I) compounds with bidentate phosphane ligands

The copper(I) compounds [Cu(dppe)2]X [X = BF4-, I-; dppe = 1,2- bis(diphenylphosphanyl)ethane], [Cu(dppp)2]X [X = BF4-, I-; dppp = 1,3- bis(diphenylphosphanyl)propane], [Cu2(dppe)3I2], and [Cu2(dppe)2I2] have been prepared and their structural properties in solution and in the solid state have been determined. 1H-, 13C-, and 31P-NMR spectra in solution [variable temperature and anion (I-) concentrations] and analyses of solids (mass spectra, elemental analyses, and CPMAS 31P-NMR spectra) are interpreted with equilibria in solution that involve two mono- and two dinuclear species. The structures of [Cu(dppe)2]CIO4, [Cu(dppp)2]BF4, and [Cu2(dppe)3I2] · 2 CHCI3 have been analyzed by X-ray crystallography. In all three structures the copper(I) center adopts a distorted tetrahedral geometry.

Heteroleptic copper(I) complexes prepared from phenanthroline and bis-phosphine ligands

Preparation of [Cu(NN)(PP)]+ derivatives has been systematically investigated starting from two libraries of phenanthroline (NN) derivatives and bis-phosphine (PP) ligands, namely, (A) 1,10-phenanthroline (phen), neocuproine (2,9-dimethyl-1,10-phenanthroline, dmp), bathophenanthroline (4,7-diphenyl-1,10-phenanthroline, Bphen), 2,9-diphenethyl-1,10-phenanthroline (dpep), and 2,9-diphenyl-1,10-phenanthroline (dpp); (B) bis(diphenylphosphino) methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3- bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)benzene (dppb), 1,1′-bis(diphenylphosphino)ferrocene (dppFc), and bis[(2- diphenylphosphino)phenyl] ether (POP). Whatever the bis-phosphine ligand, stable heteroleptic [Cu(NN)(PP)]+ complexes are obtained from the 2,9-unsubstituted-1,10-phenanthroline ligands (phen and Bphen). By contrast, heteroleptic complexes obtained from dmp and dpep are stable in the solid state, but a dynamic ligand exchange reaction is systematically observed in solution, and the homoleptic/heteroleptic ratio is highly dependent on the bis-phosphine ligand. Detailed analysis revealed that the dynamic equilibrium resulting from ligand exchange reactions is mainly influenced by the relative thermodynamic stability of the different possible complexes. Finally, in the case of dpp, only homoleptic complexes were obtained whatever the bis-phosphine ligand. Obviously, steric effects resulting from the presence of the bulky phenyl rings on the dpp ligand destabilize the heteroleptic [Cu(NN)(PP)]+ complexes. In addition to the remarkable thermodynamic stability of [Cu(dpp)2]BF4, this negative steric effect drives the dynamic complexation scenario toward almost exclusive formation of homoleptic [Cu(NN)2]+ and [Cu(PP)2]+ complexes. This work provides the definitive rationalization of the stability of [Cu(NN)(PP)]+ complexes, marking the way for future developments in this field.