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Pulsed-field ionization electron spectroscopy of group 6 metal (Cr, Mo, and W) bis(benzene) sandwich complexes.

Author
Abstract
:

Group 6 metal bis(benzene) sandwich complexes (M-bz(2): M=Cr, Mo, and W and bz=C(6)H(6)) were produced with laser vaporization molecular beam techniques and studied by pulsed-field ionization zero electron kinetic energy spectroscopy and density functional theory calculations. Each sandwich complex is in a D(6h) eclipsed configuration with (1)A(1g) and (2)A(1g) as the neutral and cationic ground electronic states, respectively. The adiabatic ionization energies for Cr-, Mo-, and W-bz(2) are measured to be 44,081(7), 44,581(10), and 43,634(7) cm(-1), respectively. The metal-benzene stretch and benzene torsion frequencies of the ion are measured to be 264, 277, and 370 cm(-1) and 11, 21, and 45 cm(-1) for Cr-, Mo-, and W-bz(2), respectively. In addition, a C-H out-of-plane bending mode is measured to be 787 cm(-1) for the Cr(+)-bz(2) complex, while a C-C in-plane bending mode is measured to be 614 cm(-1) for the W(+)-bz(2) complex. The unusual trend in the ionization energy and metal-benzene stretch frequency indicates strong relativistic effects on tungsten binding.

Year of Publication
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2006
Journal
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The Journal of chemical physics
Volume
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124
Issue
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13
Number of Pages
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134305
Date Published
:
2006
ISSN Number
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0021-9606
URL
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https://doi.org/10.1063/1.2186307
DOI
:
10.1063/1.2186307
Short Title
:
J Chem Phys
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