Exclusive Csp(3)-Csp(3) vs Csp(2)-Csp(3) Reductive Elimination from Pt(IV) Governed by Ligand Constraints.
J Am Chem Soc
; 137(51): 16004-7, 2015 Dec 30.
Article
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| MEDLINE
| ID: mdl-26673642
ABSTRACT
Selective reductive elimination of ethane (Csp(3)-Csp(3) RE) was observed following bromide abstraction and subsequent thermolysis of a Pt(IV) complex bearing both Csp(3)- and Csp(2)-hybridized hydrocarbyl ligands. Through a comparative experimental and theoretical study with two other Pt(IV) complexes featuring greater conformational flexibility of the ligand scaffold, we show that the rigidity of a meridionally coordinating ligand raises the barrier for Csp(2)-Csp(3) RE, resulting in unprecedented reactivity.
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