Electronic Structure and Photochemical Reactivity of Binuclear Metal Complexes

Citation

Smith, David Charles (1989) Electronic Structure and Photochemical Reactivity of Binuclear Metal Complexes. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/q1gz-dn84. https://resolver.caltech.edu/CaltechTHESIS:11052009-142520920

Abstract

A valence bond (VB) "weak coupling" model of the electronic structure for [Ir₂(TMB)₄](B(C₆H₅)₄)₂ is developed and generalized to the class of dimeric systems in which the metals are nonbonded, in a formal sense, and can be viewed as weakly coupled. With the VB model, the energies and widths of the previously observed optical absorption bands can be rationalized; in addition, plausible assignments are made for bands that were not interpreted satisfactorily or not observed in earlier work. The VB model does not change any of the molecular orbital-based interpretations of the thermal chemistry, photochemistry, or photophysics of these systems.

Photophysical characterization of the ^1,3(dσ^*pσ) excited state of Ir₂(TMB)₄²⁺ finds a system quite comparable to other binuclear d⁸ complexes. Both fluorescence (λₘₐₓ 735 nm, τ ~ 70 ± 30 ps) and phosphorescence (λₘₐₓ 1080 nm, τ = 210 ± 20 ns) are observed.

The relatively long lifetime of the ³(dσ^*pσ) excited state of Ir₂(TMB)₄²⁺ suggests that it should be able to participate in bimolecular photochemical reactions. The diradical-like structure of the excited state, an electron (or oxidizing hole) localized on the exterior of the M₂ unit (the dσ^* orbital) and an electron localized in the interior of the dimer cage (the pσ orbital), implies that one-electron chemistry will be observed. Reactions of the ground state follow two-electron pathways, similar to those observed for mononuclear d⁸ complexes.

The ³(dσ^*pσ) excited state of Ir₂(TMB)₄²⁺ is found to be a powerful reductant, E⁰(Ir₂(TMB)₄^3+/3(Ir₂(TMB)₄²⁺)^*) ~ 1.0 V (SSCE). Excited-state electron- transfer quenching by pyridinium acceptors is observed to follow classical Marcus theory for outer-sphere electron transfer. No "inverted" behavior is found. The bimolecular electron-transfer reaction is highly nonadiabatic, κ ~ 0.0001, because of the large donor-acceptor separation, ~ 8 Å. The results for Ir₂(TMB)₄²⁺ are discussed in comparison to those for [Ir(µ-pz)COD]₂.

Ir₂(TMB)₄²⁺ is found to react photochemically with alkyl halides. Although the ³(dσ^*pσ) excited state is a good reductant, outer-sphere electron transfer seems unlikely (E⁰(RX/RX^•-) < -1.5 V (SSCE)). An S_RN1 pathway has been suggested to explain the alkyl halide photoreduction reaction observed for metal complexes with E⁰(M₂^+/3M₂^*) < -1.5 V (SSCE); however, atom transfer to the ³(dσ^*pσ) excited state is the favored reaction mechanism for the alkyl halide photoreduction reaction of Ir₂(TMB)₄²⁺. The generality of this reaction is discussed.

While there is some ambiguity as to the primary photoprocess for alkyl halide photoreactivity, ³(dσ^*pσ) excited-state hydrogen-atom transfer has been established as the mechanism of the reaction of Ir₂(TMB)₄²⁺ and a number of organic substrates. The atom-transfer reactivity of the ³(dσ^*pσ) excited state is attributed to the presence of a hole in the dσ^* orbital, analogous to the ³nπ^* state of organic ketones. Interaction of the oxidizing hole with the electron pair of the C-H bond is the presumed pathway.

Electrochemical oxidation of Rh₂(TMB)₄²⁺ generates the d⁸-d⁷ species Rh₂(TMB)₄³⁺. This complex reacts with 1,4-cyclohexadiene to abstract a hydrogen atom mimicking the initial step of the ³(dσ^*pσ) photoreaction. The importance of this result is discussed in terms of energy storage systems and extension of the range of hydrocarbon oxidations with binuclear d⁸ complexes.

The d⁷-d⁷ dihydride product obtained from the photoreaction of Ir₂(TMB)₄²⁺ and 1,4-cyclohexadiene is isolated and characterized. In addition to NMR, UV-Vis, IR, and Raman spectra, the complex is characterized crystallographically. The reactivity of this complex is also discussed.

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