Closed-Shell Molecules That Ionize More Readily Than Cesium-Reference-Cited by-同舟云学术

Closed-Shell Molecules That Ionize More Readily Than Cesium

Published:2002-12-06 Issue:5600 Volume:298 Page:1971-1974
ISSN:0036-8075
Container-title:Science
language:en
Short-container-title:Science

Author:

Cotton F. Albert¹,Gruhn Nadine E.²,Gu Jiande³,Huang Penglin¹,Lichtenberger Dennis L.²,Murillo Carlos A.¹,Van Dorn Laura O.²,Wilkinson Chad C.¹

Affiliation:

1. Department of Chemistry and Laboratory for Molecular Structure and Bonding, Texas A&M University, Post Office Box 30012, College Station, TX 77842–3012, USA.

2. Department of Chemistry and Laboratory for Gas-Phase Electron Spectroscopy, The University of Arizona, Tucson, AZ 85721, USA.

3. Drug Design and Discovery Center, State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Shanghai Institutes for Biological Sciences, Chinese Academy of Sciences, Shanghai 200031, China.

Abstract

We report a class of molecules with extremely low ionization enthalpies, one member of which has been determined to have a gas-phase ionization energy (onset, 3.51 electron volts) lower than that of the cesium atom (which has the lowest gas-phase ionization energy of the elements) or of any other known closed-shell molecule or neutral transient species reported. The molecules are dimetal complexes with the general formula M 2 (hpp) 4 (where M is Cr, Mo, or W, and hpp is the anion of 1,3,4,6,7,8-hexahydro-2 H -pyrimido[1,2- a ]pyrimidine), structurally characterized in the solid state, spectroscopically characterized in the gas phase, and modeled with theoretical computations. The low-energy ionization of each molecule corresponds to the removal of an electron from the delta bonding orbital of the quadruple metal-metal bond, and a strong interaction of this orbital with a filled orbital on the hpp ligands largely accounts for the low ionization energies.

Publisher

American Association for the Advancement of Science (AAAS)

Subject

Multidisciplinary

Reference39 articles.

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4. It is to be emphasized that the molecules reported here are real molecules which can be made in gram quantities and stored in inert atmosphere at room temperature indefinitely. Previous discussions of so-called “superalkali” compounds are purely theoretical discussions of molecules not known to exist (5 6).

5. Gutsev G. L., Boldyrev A. I., Chem. Phys. Lett. 9, 262 (1982).

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