Pulsed-field ionization electron spectroscopy of group 6 metal (Cr, Mo, and W) bis(benzene) sandwich complexes.
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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 | :
2006
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Journal | :
The Journal of chemical physics
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Volume | :
124
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Issue | :
13
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Number of Pages | :
134305
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Date Published | :
2006
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ISSN Number | :
0021-9606
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URL | :
https://doi.org/10.1063/1.2186307
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DOI | :
10.1063/1.2186307
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Short Title | :
J Chem Phys
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