The coordination chemistry of copper(i) in liquid ammonia, trialkyl and triphenyl phosphite, and tri-n-butylphosphine solution

Abstract

The coordination chemistry of the solvate complexes of the relatively soft electron-pair acceptor copper(I) has been studied in solution and solid state in seven solvents with strong electron-pair donor properties, liquid ammonia, trimethyl, triethyl, triisopropyl, tri-n-butyl and triphenyl phosphite, and tri-n-butylphosphine. The solvate complexes have been characterised by means of EXAFS and 63Cu NMR spectroscopy, and in some cases also by 65Cu NMR spectroscopy. The copper(I) ion is three-coordinated, most probably in a coplanar trigonal fashion, in liquid ammonia with a mean Cu-N bond distance of 2.00(1) Angstroms. No 63Cu NMR signal has been detected from the ammonia solvated copper(I) ion in liquid ammonia, which supports a three-coordination. The phosphite and phosphine solvated copper(I) ions are tetrahedral with Cu-P bond distances in the range 2.24-2.28 Angstrom in both solution and solid state as determined by EXAFS spectroscopy. The tetrahedral configuration of these complexes has been confirmed by 63Cu and 65Cu NMR spectroscopy through the J(63Cu-31P) and J(65Cu-31P) couplings. The fact that two of the investigated complexes, [Cu(P(OC6H5)3)4]+ and [Cu(P(C4H9)3)4]+, are 63Cu and 65Cu NMR silent is probably caused by a significantly angular distorted tetrahedral configuration.

Investigation of the Structural and Dynamical Properties of Cu⁺ in Liquid Ammonia: A Quantum Mechanical Charge Field (QMCF) Molecular Dynamics Study

“…4, the geometry complex that was formed in the first solvation shell is tetrahedral. These data have good agreement with the experiments of EXAFS and IR Photodissociation [7][8]. A similar conclusion can be drawn from the vibrational frequency of the Cu + -N interaction obtained via VACFs and subsequent Fourier Transform (FT) which is depicted in Fig.…”

“…4. The result of coordination number has excellent agreement IR photodissociation spectroscopy [7] although the three-coordinated complex was showed via EXAFS [8]. Further comparisons of structural properties of Cu + complexes in various methods are listed in Table 1.…”

“…The average distance of Cu-N is 2.004 Å [8]. The stability of Cu-NH3 complex system also has been calculated via the dissociation energy using ion beam mass spectrometer.…”

The solvation of the mercury(II) ion—a199Hg NMR study

“…N,N-Dimethylthioformamide, (CH 3 2 NCHS, was prepared from phosphorus pentasulfide, P 2 S 5 , (Merck) and N,N-dimethylformamide, (CH 3 2 NCHO, (Merck) as described by Gutmann. 11 Liquid ammonia, NH 3 (l), was distilled from 25% aqueous ammonia (Analytical grade, Merck), as described in detail elsewhere, 12 and used within some hours. Millipore filtered deionised water was used throughout this study.…”

Growth of sphere- and tetrapod-shaped Cd(Cu)Se nanocrystals from Cu(C17H35COO)2 and Cu4(PPh3)4(μ3-I)4

“…It is found to be ~20, which means most of copper stearate remains unreacted, probably due to formation of Cu complexes with phosphines. 12 The most interesting property of the samples obtained is the intense (QY up to 5-10%) copper-related IR emission at 700-900 nm. Time-resolved measurements 10 showed a 0.5-1 μs lifetime; thus, Cd(Cu)Se are perspective for use in biotags.…”