The X-ray photoelectron spectra of some forty-six copper compounds and complexes have been measured. The chemical shifts obtained from accurate determinations of the binding energies have been qualitatively explained on the basis of the Pauling electronegativity concept using the group electronegatives of Huheey for the polyatomic counter anions. The chemical shifts of the copper atoms as well as the atoms in the ligands were found to be dependent not only on the oxidation state but also on the kind and number of ligand atoms. Intense satellite lines were found in the 2p and 2s bands of the cupric compounds; the number and splitting of the satellites were found to be sensitive to the chemical environment. A correlation was found between the satellite splitting and the binding energies and this is explained by a 3d→4s, 4p ‘shake-up’ mechanism.

X-ray photoelectron spectroscopy of copper compounds

The CNDO‐II approximate SCF molecular orbital method is extended to include molecules containing atoms of the first transition series. Valence orbitals explicitly considered in the transition atoms are 3d, 4s, and 4p. Calculations are reported for the monoxides of Sc, Ti, V, and Cu, using three sets of orbital exponents. The results are compared, where possible, with those obtained by ab initio methods, and appropriate values for off‐diagonal core parameters are proposed. The method is used to evaluate the orbital levels for a number of hexafluorometallate complex ions. Fair agreement is found between the calculated and experimentally observed metal‐fluorine equilibrium bond lengths. The eigenfunctions are used to obtain the transferred spin densities to the fluorine ligands and in general these compare favourably with the values derived from electron spin and nuclear magnetic resonance measurements.

All-Valence Electron CNDO Calculations on Transition Metal Complexes

Multiply charged anions are common in the condensed phase, and their existence has been generally taken for granted. But until very recently, these species have only rarely been observed in the gas phase. A new experimental technique, using photodetachment photoelectron spectroscopy, electrospray, and ion-trap mass spectrometry, has been developed in the author's laboratory to probe multiply charged anions in the gas phase. In this article, the principles of this technique and some of the initial results will be presented and discussed. The difference between photodetachment of singly and multiply charged anions is emphasized. Photodetachment photoelectron spectroscopy is ideal to probe the chemical and physical properties of free multiply charged anions. Among the initial findings, the repulsive Coulomb barriers existing in multiply charged anions have been directly observed. The relationship between the intramolecular electron−electron repulsion and the potential barrier is elucidated, culminating in th...

Probing Free Multiply Charged Anions Using Photodetachment Photoelectron Spectroscopy

The Chemistry of the Dithioacid and 1,1‐Dithiolate Complexes

Molecular orbital analysis of the bonding in low nuclearity gold and platinum tertiary phosphine complexes and the development of isolobal analogies for the M(PR3) fragment

Molecular orbital calculations for complexes of heavier transition elements. I. Parameter variations in the case of tetrachloroplatinate(II)

Molecular orbital calculations for complexes of heavier transition elements. III. The metal-metal bonding and electronic structure of Re2Cl82-

Extended Hueckel calculations of the molecular orbitals in bis(.beta.-ketoenolate) complexes of copper(II) and nickel(II)

Molecular orbital calculations for complexes of heavier transition elements. II. Hexachloro complexes of tetravalent rhenium, osmium, iridium, and platinum

. The 59Co pure nuclear quadrupole resonance spectra of a series of trigonally coordinated cobalt complexes, MX 3 CO(CO)4' where M = Si, Ge, Sn, Pd, and X = Cl, Br, I, and 65 are reported. The 35,37 Cl quadrupo,le resonance in SiCl 3 Co(CO)4 are also reported. The variation in field eradients obtained from the quadrupole coupling constants in these molecules can be interpreted in terms of a and ~ bonding of MX3 to the cobalt. In certain cases explicit a or ~ effects can be separated. 'Finally, strong evidence for the existence of Si-Cl d~-p~ bonding is presented. (1) Paper III in the series Transition Metal Nuclear Quadrupole Resonance by CBH and co-workers. (2) a. Noyes Chemical Laboratory, University of IllinOis, Urbana, 61801. b. Department of Chemistry, University of California, Berkeley •. (3) To whom correspondence and reprint requests should be addressed.

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Charles Bonner Harris

Papers

Molecular orbital calculations for complexes of heavier transition elements. I. Parameter variations in the case of tetrachloroplatinate(II)

Molecular orbital calculations for complexes of heavier transition elements. III. The metal-metal bonding and electronic structure of Re2Cl82-

Extended Hueckel calculations of the molecular orbitals in bis(.beta.-ketoenolate) complexes of copper(II) and nickel(II)

Molecular orbital calculations for complexes of heavier transition elements. II. Hexachloro complexes of tetravalent rhenium, osmium, iridium, and platinum

Pure nuclear quadrupole resonance spectrum of cobalt-59 in adducts of cobalt tetracarbonyl, MX3Co(CO)4