Exclusive Csp3–Csp3 vs Csp2–Csp3 Reductive Elimination from PtIV Governed by Ligand Constraints

Selective reductive elimination of ethane (Csp3-Csp3 RE) was observed following bromide abstraction and subsequent thermolysis of a PtIV complex bearing both Csp3- and Csp2-hybridized hydrocarbyl ligands. Through a comparative experimental and theoretical study with two other PtIV complexes featuring greater conformational flexibility of the ligand scaffold, we show that the rigidity of a meridionally coordinating ligand raises the barrier for Csp2-Csp3 RE, resulting in unprecedented reactivity.