Spectroscopic and theoretical studies of binuclear molybdenum(II) carboxylates

Mark C. Manning; Gary F. Holland; Donald E Ellis; William C. Trogler

doi:10.1021/j100239a025

Spectroscopic and theoretical studies of binuclear molybdenum(II) carboxylates

Mark C. Manning, Gary F. Holland, Donald E Ellis^*, William C. Trogler

^*Corresponding author for this work

Physics and Astronomy

Research output: Contribution to journal › Article › peer-review

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Abstract

Electronic absorption spectra of Mo₂(O₂CCF₃)₄ and Mo₂(O₂CH)₄ have been measured at 10 K in inert matrices. Results are compared with previous studies of Mo₂(O₂CCH₃)₄. Raman spectra of the three carboxylate complexes have been measured and assigned. Unlike Mo₂Cl₈ ^4- or Re₂Cl₈ ^2- resonance enhancement of the metal-metal stretch did not occur when the lowest energy absorption band was irradiated; preresonance enhancement of a carboxylate stretching vibration did occur. Certain aspects of the SCF-Xα-DV calculations for Mo₂(O₂CH)₄ agree better with previous HF calculations than with SCF-Xα-SW results. The sensitivity of the π-π* separation to metal-metal distance may explain these differences. Energies of both the singlet and triplet δ → δ*, δ → π*, σ → δ*, and δ → π* (OCO) transitions have been calculated and compared with the optical spectra.

Original language	English (US)
Pages (from-to)	3083-3088
Number of pages	6
Journal	Journal of Physical Chemistry
Volume	87
Issue number	16
DOIs	https://doi.org/10.1021/j100239a025
State	Published - Jan 1 1983

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Engineering(all)
Physical and Theoretical Chemistry

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title = "Spectroscopic and theoretical studies of binuclear molybdenum(II) carboxylates",

abstract = "Electronic absorption spectra of Mo2(O2CCF3)4 and Mo2(O2CH)4 have been measured at 10 K in inert matrices. Results are compared with previous studies of Mo2(O2CCH3)4. Raman spectra of the three carboxylate complexes have been measured and assigned. Unlike Mo2Cl8 4- or Re2Cl8 2- resonance enhancement of the metal-metal stretch did not occur when the lowest energy absorption band was irradiated; preresonance enhancement of a carboxylate stretching vibration did occur. Certain aspects of the SCF-Xα-DV calculations for Mo2(O2CH)4 agree better with previous HF calculations than with SCF-Xα-SW results. The sensitivity of the π-π* separation to metal-metal distance may explain these differences. Energies of both the singlet and triplet δ → δ*, δ → π*, σ → δ*, and δ → π* (OCO) transitions have been calculated and compared with the optical spectra.",

author = "Manning, {Mark C.} and Holland, {Gary F.} and Ellis, {Donald E} and Trogler, {William C.}",

year = "1983",

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doi = "10.1021/j100239a025",

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journal = "Journal of Physical Chemistry",

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T1 - Spectroscopic and theoretical studies of binuclear molybdenum(II) carboxylates

AU - Manning, Mark C.

AU - Holland, Gary F.

AU - Ellis, Donald E

AU - Trogler, William C.

PY - 1983/1/1

Y1 - 1983/1/1

N2 - Electronic absorption spectra of Mo2(O2CCF3)4 and Mo2(O2CH)4 have been measured at 10 K in inert matrices. Results are compared with previous studies of Mo2(O2CCH3)4. Raman spectra of the three carboxylate complexes have been measured and assigned. Unlike Mo2Cl8 4- or Re2Cl8 2- resonance enhancement of the metal-metal stretch did not occur when the lowest energy absorption band was irradiated; preresonance enhancement of a carboxylate stretching vibration did occur. Certain aspects of the SCF-Xα-DV calculations for Mo2(O2CH)4 agree better with previous HF calculations than with SCF-Xα-SW results. The sensitivity of the π-π* separation to metal-metal distance may explain these differences. Energies of both the singlet and triplet δ → δ*, δ → π*, σ → δ*, and δ → π* (OCO) transitions have been calculated and compared with the optical spectra.

AB - Electronic absorption spectra of Mo2(O2CCF3)4 and Mo2(O2CH)4 have been measured at 10 K in inert matrices. Results are compared with previous studies of Mo2(O2CCH3)4. Raman spectra of the three carboxylate complexes have been measured and assigned. Unlike Mo2Cl8 4- or Re2Cl8 2- resonance enhancement of the metal-metal stretch did not occur when the lowest energy absorption band was irradiated; preresonance enhancement of a carboxylate stretching vibration did occur. Certain aspects of the SCF-Xα-DV calculations for Mo2(O2CH)4 agree better with previous HF calculations than with SCF-Xα-SW results. The sensitivity of the π-π* separation to metal-metal distance may explain these differences. Energies of both the singlet and triplet δ → δ*, δ → π*, σ → δ*, and δ → π* (OCO) transitions have been calculated and compared with the optical spectra.

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Spectroscopic and theoretical studies of binuclear molybdenum(II) carboxylates

Abstract

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