Laser spectroscopy of open-shell sandwich complexes

• Published in: Coordination chemistry reviews Vol. 111; pp. 111 - 116
• Main Authors: Perutz, Robin N., Hill, Jeremy N., McCamley, Andrew
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 06.12.1991
• ISSN: 0010-8545; 1873-3840
• DOI: 10.1016/0010-8545(91)84015-W

Emission and excitation spectra of the metallocenes, Cp 2M (M = Re, Mo, W) and Cp * 2Re (Cp = η 5-C 5H 5 Cp * = η 5-C 5Me 5) isolated in N 2and Ar matrices at 12 K have been excited by low-power irradiation with a tunable pulsed laser into their lowest LMCT bands. This method generates vibrationally resolved spectra which are much sharper than their absorption counterparts because the laser selects individual conformers or matrix trapping sites of the guest molecule. Emission lifetimes of 72 and 3.6 ns have been measured for Cp 2Re and Cp * 2Re respectively. The arene sandwich complexes, V(η 6-C 6H 6) 2 and V(η 6-1,3,5-C 6H 3Me 3) 2, respond differently to laser irradiation yielding resonance Raman spectra with long vibrational progressions.