A new era of LMCT: leveraging ligand-to-metal charge transfer excited states for photochemical reactions

Abstract

Ligand-to-metal charge transfer (LMCT) excited states showcase promise in enabling photochemical reactions. This article details design principles to enable low energy LMCT excited states and notable examples that drivereactions from these states.

Dinitrogen activation at chromium by photochemically induced CrII–C bond homolysis

“…Next, we examined visible-light photolysis to promote homolytic Cr–C bond cleavage. 15 Photochemically induced bond cleavage is not uncommon; 16 however, the photoinduced loss of an organic moiety and the subsequent binding and activation of N 2 at a metal centre is rare. In the singular example with an azophilic early transition metal, Chirik and co-workers showed the photochemically induced reductive elimination of ( p -Tol)–( p -Tol) from [(η 5 -C 5 H 5 ) 2 Zr( p -Tol) 2 ] generated the dinuclear side-on bound dinitrogen complex [{(η 5 -C 5 Me 4 H) 2 Zr} 2 ( μ 2 ,η 2 ,η 2 -N 2 )].…”