Connecting binuclear Pd(III) and mononuclear Pd(IV) chemistry by Pd-Pd bond cleavage

David C. Powers; Eunsung Lee; Alireza Ariafard; Melanie S. Sanford; Brian F. Yates; Allan J. Canty; Tobias Ritter

doi:10.1021/ja304401u

Connecting binuclear Pd(III) and mononuclear Pd(IV) chemistry by Pd-Pd bond cleavage

David C. Powers, Eunsung Lee, Alireza Ariafard, Melanie S. Sanford, Brian F. Yates^*, Allan J. Canty, Tobias Ritter

^*Corresponding author for this work

Research School of Chemistry

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

145 Citations (Scopus)

Abstract

Oxidation of binuclear Pd(II) complexes with PhICl ₂ or PhI(OAc) ₂ has previously been shown to afford binuclear Pd(III) complexes featuring a Pd-Pd bond. In contrast, oxidation of binuclear Pd(II) complexes with electrophilic trifluoromethylating ("CF ₃ ⁺") reagents has been reported to afford mononuclear Pd(IV) complexes. Herein, we report experimental and computational studies of the oxidation of a binuclear Pd(II) complex with "CF ₃ ⁺" reagents. These studies suggest that a mononuclear Pd(IV) complex is generated by an oxidation-fragmentation sequence proceeding via fragmentation of an initially formed, formally binuclear Pd(III), intermediate. The observation that binuclear Pd(III) and mononuclear Pd(IV) complexes are accessible in the same reactions offers an opportunity for understanding the role of nuclearity in both oxidation and subsequent C-X bond-forming reactions.

Original language	English
Pages (from-to)	12002-12009
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	134
Issue number	29
DOIs	https://doi.org/10.1021/ja304401u
Publication status	Published - 25 Jul 2012

Access to Document

10.1021/ja304401u

Cite this

@article{6107f79b4fc84539bb55770fa6f54c0e,

title = "Connecting binuclear Pd(III) and mononuclear Pd(IV) chemistry by Pd-Pd bond cleavage",

abstract = "Oxidation of binuclear Pd(II) complexes with PhICl 2 or PhI(OAc) 2 has previously been shown to afford binuclear Pd(III) complexes featuring a Pd-Pd bond. In contrast, oxidation of binuclear Pd(II) complexes with electrophilic trifluoromethylating ({"}CF 3 +{"}) reagents has been reported to afford mononuclear Pd(IV) complexes. Herein, we report experimental and computational studies of the oxidation of a binuclear Pd(II) complex with {"}CF 3 +{"} reagents. These studies suggest that a mononuclear Pd(IV) complex is generated by an oxidation-fragmentation sequence proceeding via fragmentation of an initially formed, formally binuclear Pd(III), intermediate. The observation that binuclear Pd(III) and mononuclear Pd(IV) complexes are accessible in the same reactions offers an opportunity for understanding the role of nuclearity in both oxidation and subsequent C-X bond-forming reactions.",

author = "Powers, {David C.} and Eunsung Lee and Alireza Ariafard and Sanford, {Melanie S.} and Yates, {Brian F.} and Canty, {Allan J.} and Tobias Ritter",

year = "2012",

month = jul,

day = "25",

doi = "10.1021/ja304401u",

language = "English",

volume = "134",

pages = "12002--12009",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "29",

}

TY - JOUR

T1 - Connecting binuclear Pd(III) and mononuclear Pd(IV) chemistry by Pd-Pd bond cleavage

AU - Powers, David C.

AU - Lee, Eunsung

AU - Ariafard, Alireza

AU - Sanford, Melanie S.

AU - Yates, Brian F.

AU - Canty, Allan J.

AU - Ritter, Tobias

PY - 2012/7/25

Y1 - 2012/7/25

N2 - Oxidation of binuclear Pd(II) complexes with PhICl 2 or PhI(OAc) 2 has previously been shown to afford binuclear Pd(III) complexes featuring a Pd-Pd bond. In contrast, oxidation of binuclear Pd(II) complexes with electrophilic trifluoromethylating ("CF 3 +") reagents has been reported to afford mononuclear Pd(IV) complexes. Herein, we report experimental and computational studies of the oxidation of a binuclear Pd(II) complex with "CF 3 +" reagents. These studies suggest that a mononuclear Pd(IV) complex is generated by an oxidation-fragmentation sequence proceeding via fragmentation of an initially formed, formally binuclear Pd(III), intermediate. The observation that binuclear Pd(III) and mononuclear Pd(IV) complexes are accessible in the same reactions offers an opportunity for understanding the role of nuclearity in both oxidation and subsequent C-X bond-forming reactions.

AB - Oxidation of binuclear Pd(II) complexes with PhICl 2 or PhI(OAc) 2 has previously been shown to afford binuclear Pd(III) complexes featuring a Pd-Pd bond. In contrast, oxidation of binuclear Pd(II) complexes with electrophilic trifluoromethylating ("CF 3 +") reagents has been reported to afford mononuclear Pd(IV) complexes. Herein, we report experimental and computational studies of the oxidation of a binuclear Pd(II) complex with "CF 3 +" reagents. These studies suggest that a mononuclear Pd(IV) complex is generated by an oxidation-fragmentation sequence proceeding via fragmentation of an initially formed, formally binuclear Pd(III), intermediate. The observation that binuclear Pd(III) and mononuclear Pd(IV) complexes are accessible in the same reactions offers an opportunity for understanding the role of nuclearity in both oxidation and subsequent C-X bond-forming reactions.

UR - http://www.scopus.com/inward/record.url?scp=84864218590&partnerID=8YFLogxK

U2 - 10.1021/ja304401u

DO - 10.1021/ja304401u

M3 - Article

AN - SCOPUS:84864218590

SN - 0002-7863

VL - 134

SP - 12002

EP - 12009

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 29

ER -

Connecting binuclear Pd(III) and mononuclear Pd(IV) chemistry by Pd-Pd bond cleavage

Abstract

Access to Document

Other files and links

Fingerprint

Cite this