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

Eric G. Bowes; Shrinwantu Pal; Jennifer A. Love

doi:10.1021/jacs.5b10993

Exclusive Csp³-Csp³ vs Csp²-Csp³ Reductive Elimination from Pt^IV Governed by Ligand Constraints

Eric G. Bowes
, Shrinwantu Pal
, Jennifer A. Love

Research output: Contribution to journal › Article › peer-review

34 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	16004-16007
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	137
Issue number	51
DOIs	https://doi.org/10.1021/jacs.5b10993
State	Published - Dec 30 2015
Externally published	Yes

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abstract = "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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AU - Love, Jennifer A.

PY - 2015/12/30

Y1 - 2015/12/30

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/84953439950

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DO - 10.1021/jacs.5b10993

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JF - Journal of the American Chemical Society

IS - 51

ER -

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

Abstract

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Exclusive Csp³-Csp³ vs Csp²-Csp³ Reductive Elimination from Pt^IV Governed by Ligand Constraints