Solid-State and Solution Structural Properties of Copper(I) Compounds with Bidentate Phosphane Ligands

Abstract

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]ClO4, [Cu(dppp)2]BF4, and [Cu2(dppe)3I2] · 2 CHCl3 have been analyzed by X‐ray crystallography. In all three structures the copper(I) center adopts a distorted tetrahedral geometry.

Synthesis, X‐Ray Structures, and Fluxional Properties of Symmetrical, Asymmetrical Binuclear and Cubane Type Copper(I) Complexes Bearing the Pyrrole‐Based P, N‐Hetero Donor Ligand

“…Similar equilibrium involving monodentate and bridging mode of ligand 1,6‐bis(diphenylphosphino)hexane has been reported for the dimeric copper(I) complex . Comba and co‐workers have reported equilibria with mono‐ and dinuclear copper(I) complexes supported by 1,2‐bis(diphenylphosphanyl)ethane . The existence of equilibrium between [Cu 2 (dppp) 2 X 2 ] and [Cu(dppp) 2 ]X (dppp=1,3‐bis(diphenylphosphino)propane; X=halides) have been reported by Pettinari et al .…”

Copper(I) binap complexes (binap=(2,2′-bis(diphenylphosphino)-1,1′-binaphthyl). Luminescence from IL and LLCT states

“…[ [17] and [Cu(P-P)I] 2 [18] with P-P = bidentate bis-arylphosphine. The dimers are composed of tetrahedral Cu I (P-P)I 2 monomers which are bridged by iodide [18].…”

E4 Butterfly Complexes (E=P, As) as Chelating Ligands

“…Thec oordination sphere of copper is completed by one acetonitrile ligand, resulting in at rigonalplanar arrangement ( Figure 4). This is slightly longer than in the archetypal compound [(dppe) 2 Cu] + [ClO 4 ] À (2.259(2) -2.301(2) ; dppe = bis(diphenylphosphino)ethane) [11] but compares well to the bond lengths in the dppmcontaining compound [(dppm)(POP)Cu] + [BF 4 ] À (POP = bis [2-(diphenylphosphino)phenyl]ether; dppm = bis(diphenylphosphino)methane) with 2.333(3) and 2.425(4) . This is slightly longer than in the archetypal compound [(dppe) 2 Cu] + [ClO 4 ] À (2.259(2) -2.301(2) ; dppe = bis(diphenylphosphino)ethane) [11] but compares well to the bond lengths in the dppmcontaining compound [(dppm)(POP)Cu] + [BF 4 ] À (POP = bis [2-(diphenylphosphino)phenyl]ether; dppm = bis(diphenylphosphino)methane) with 2.333(3) and 2.425(4) .…”