Probing the primary processes of a triazido-cobalt(III) complex with femtosecond vibrational and electronic spectroscopies. Photochemical selectivity and multi-state reactivity.

The elementary dynamics following 355 nm-excitation of the complex, mer-[Co(dien)(N3)3], were studied in liquid dimethyl sulfoxide (DMSO) solution using femtosecond-ultraviolet-pump/mid-infrared-to-near-ultraviolet probe spectroscopy in conjunction with electronic structure calculations based on density functional theory. Following the initial N3--to-Co charge transfer excitation, the parent complex undergoes an ultrafast metal-to-ligand back electron transfer (BET) within 2 ps thereby populating a metal-centered singlet excited state, 1MC, which can either repopulate the electronic ground state or cleave an azido ligand from the ligand sphere surrounding the metal center. From the asymptotic ground-state bleaching signal after 1 ns, a primary quantum yield for ligand loss of ca. 13% is estimated. The IR-spectrum of the product demonstrates that the photodissociation occurs selectively from the equatorial binding site thereby leading exclusively to the solvolysis product, mer-trans-[Co(dien)(N3)2(DMSO)]+, which features the solvent ligand in the equatorial coordination plane and the azides in the two axial positions. The remarkable photochemical selectivity is traced back to the initial BET and the nature of the intermediate state, 1MC, whose electronic structure entails occupancy of the σ-antibonding d(x2-y2)-orbital. A stereochemical scrambling at the stage of the primary penta-coordinated diazido product is kinetically inhibited on the singlet surface by an energy barrier of roughly 27 kJ mol-1. Primary penta-coordinated products that may be born on the triplet surface are funneled to their singlet ground-state preferentially from geometries with trans-oriented azido ligands thereby also preventing a stereochemical isomerization that could possibly arise from an intersystem crossing.