Laser vaporization generation of the diatomic radicals PdB, 105PdB, PdAl, and105PdAl: Electron spin resonance investigation in neon matrices at 4 K

ACS Citation

Knight, L. B.; Babb, R. M.; Hill, D. W.; McKinley, A. J. Laser vaporization generation of the diatomic radicals PdB, 105PdB, PdAl, and105PdAl: Electron spin resonance investigation in neon matrices at 4 K. J. Chem. Phys. 1992, 97, 2987-2987.

Abstract

The new diatomic radicals PdB and PdAl have been generated by depositing the products produced from the pulsed laservaporization of the elemental mixtures into neon matrices at 4 K. ESR(electron spin resonance) studies of these matrix isolated radicals, including an analysis of the 105Pd(I=5/2), 27Al(I=5/2), and 11B(I=3/2) nuclear hyperfineinteractions, show that both have X-€‰ 2Σ electronic ground states. These new results are compared with previous ESR measurements for PdH, PdCH3, YPd, ScPd, and PdH2 + to reveal electronic structure information and bonding trends as the complexity of the ligand increases 1s, 2p, 3p, 3d, and 4d. Ab initio UHF (unrestricted Hartree-Fock) theoretical calculations were also conducted on four of these small palladium radicals as part of this experimental investigation. A simple interpretation of the 105Pd hyperfineinteractions and molecular g tensors based on the degree of charge transfer to palladium is presented. The observed magnetic parameters (MHz) for 105Pd11B in a neon matrix at 4 K are g -ˆ¥=2.009(2), g -Š¥=2.042(2), A -ˆ¥=-ˆ’1483(15), and A -Š¥=-ˆ’1483(2) for 105Pd, and A -ˆ¥=197(4) and A -Š¥=140(1) for 11B. The parameters for 105Pd27Al are g -ˆ¥=2.010(1), g -Š¥=2.0343(5), A -ˆ¥=-ˆ’1283(10) and A -Š¥=-ˆ’1268(2) for 105Pd, and A -ˆ¥=182(2) and A -Š¥=84.6(5) for 27Al.

Source Name

Journal of Chemical Physics

Publication Date

1-1-1992

Volume

97

Issue

5

Page(s)

6044-6044

Document Type

Citation

Citation Type

Article

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