TIME-RESOLVED RESONANCE RAMAN-SPECTROSCOPY AT LOW-TEMPERATURE - THE EXCITED-STATE METAL-METAL STRETCHING FREQUENCY OF RH-2(TMB)(4)(2-DIMETHYL-2,5-DIISOCYANOHEXANE)() (TMB = 2,5)

The time-resolved resonance Raman spectrum of the short-lived triplet (d sigmap sigma) excited state of Rh-2(TMB)(4)(2+) (TMB = 2,5-dimethy l-2,5-diisocyanohexane) was obtained by lowering the temperature of a 3:1 ethanol/methanol solution until the excited-state lifetime became much greater than the width of the pulsed laser excitation source. The metal-metal stretching frequency is 151 cm(-1) in the excited triplet state, as compared to 50 cm(-1) in the ground state. The diatomic har monic force constants derived from these frequencies are in a 9.12:1 r atio (excited state/ground state), consistent with the simple molecula r orbital description that predicts that the Rh-Rh bond order is great er in the excited state than in the ground state. A comparison of Rh2( TMB)42+ and Rh(2)b(4)(2+) (b = 1,3-diisocyanopropane) Raman data indic ates that the nature of the bridging ligand considerably affects the g round- and excited-state metal-metal stretching frequencies and that t he population of the p sigma orbital may have very little effect on th e bonding in the excited triplet state.