Exclusive Csp<sup>3</sup>–Csp<sup>3</sup> vs Csp<sup>2</sup>–Csp<sup>3</sup> Reductive Elimination from Pt<sup>IV</sup> Governed by Ligand Constraints
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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.
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2016-02-12
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