Ultrafast infrared studies of the role of spin states in organometallic reaction dynamics.

Abstract

The importance of spin state changes in organometallic reactions is a topic of significant interest, as an increasing number of reaction mechanisms involving changes of spin state are consistently being uncovered. The potential influence of spin state changes on reaction rates can be difficult to predict, and thus this class of reactions remains among the least well understood in organometallic chemistry. Ultrafast time-resolved infrared (TRIR) spectroscopy provides a powerful tool for probing the dynamics of spin state changes in organometallic catalysis, as such processes often occur on the picosecond to nanosecond time scale and can readily be monitored in the infrared via the absorptions of carbonyl reporter ligands. In this Account, we summarize recent work from our group directed toward identifying trends in reactivity that can be used to offer predictive insight into the dynamics of coordinatively unsaturated organometallic reaction intermediates. In general, coordinatively unsaturated 16-electron (16e) singlets are able to coordinate to solvent molecules as token ligands to partially stabilize the coordinatively unsaturated metal center, whereas 16e triplets and 17-electron (17e) doublets are not, allowing them to diffuse more rapidly through solution than their singlet counterparts. Triplet complexes typically (but not always) undergo spin crossover prior to solvent coordination, whereas 17e doublets do not coordinate solvent molecules as token ligands and cannot relax to a lower spin state to do so. 16e triplets are typically able to undergo facile spin crossover to yield a 16e singlet where an associative, exothermic reaction pathway exists. The combination of facile spin crossover with faster diffusion through solution for triplets can actually lead to faster catalytic reactivity than for singlets, despite the forbidden nature of these reactions. We summarize studies on odd-electron complexes in which 17e doublets were found to display varying behavior with regard to their tendency to react with 2-electron donor ligands to form 19-electron (19e) adducts. The ability of 19e adducts to serve as reducing agents in disproportionation reactions depends on whether the excess electron density localized at the metal center or at a ligand site. The reactivity of both 16e and 17e complexes toward a widely used organic nitroxyl radical (TEMPO) are reviewed, and both classes of complexes generally react similarly via an associative mechanism with a low barrier to these reactions. We also describe recent work targeted at unraveling the photoisomerization mechanism of a thermal-solar energy storage complex in which spin state changes were found to play a crucial role. Although a key triplet intermediate was found to be required for this photoisomerization mechanism to proceed, the details of why this triplet is formed in some complexes (those based on ruthenium) and not others (those based on iron, molybdenum, or tungsten) remains uncertain, and further exploration in this area may lead to a better understanding of the factors that influence intramolecular and excited state spin state changes.