Mechanism of direct molecular oxygen insertion in a palladium(II)-hydride bond

Jason M. Keith; Richard P. Muller; Richard A. Kemp; Karen I. Goldberg; William A. Goddard; Jonas Oxgaard

doi:10.1021/ic061392z

Mechanism of direct molecular oxygen insertion in a palladium(II)-hydride bond

Jason M. Keith
, Richard P. Muller
, Richard A. Kemp
, Karen I. Goldberg
, William A. Goddard
, Jonas Oxgaard

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

Abstract

The mechanism of the direct insertion of molecular oxygen into a palladium hydride bond has been elucidated using quantum mechanics (B3LYP/LACVP* * with the PBF continuum solvent model). The key step is found to be the abstraction of the hydrogen atom resulting in the formation of a Pd ^I/HO₂ (triplet) radical pair, which then proceeds to form a singlet palladium hydroperoxo species. Potential palladium(0) pathways were explored and were found to be inaccessible. The results are in agreement with recent experimental results and are consistent with our previously predicted mechanism for an analogue system.

Original language	English
Pages (from-to)	9631-9633
Number of pages	3
Journal	Inorganic Chemistry
Volume	45
Issue number	24
DOIs	https://doi.org/10.1021/ic061392z
Publication status	Published - 27 Nov 2006
Externally published	Yes

Access to Document

10.1021/ic061392z

Cite this

@article{32a6023f70de42b8b292d4619a5b3aca,

title = "Mechanism of direct molecular oxygen insertion in a palladium(II)-hydride bond",

abstract = "The mechanism of the direct insertion of molecular oxygen into a palladium hydride bond has been elucidated using quantum mechanics (B3LYP/LACVP* * with the PBF continuum solvent model). The key step is found to be the abstraction of the hydrogen atom resulting in the formation of a Pd I/HO2 (triplet) radical pair, which then proceeds to form a singlet palladium hydroperoxo species. Potential palladium(0) pathways were explored and were found to be inaccessible. The results are in agreement with recent experimental results and are consistent with our previously predicted mechanism for an analogue system.",

author = "Keith, \{Jason M.\} and Muller, \{Richard P.\} and Kemp, \{Richard A.\} and Goldberg, \{Karen I.\} and Goddard, \{William A.\} and Jonas Oxgaard",

year = "2006",

month = nov,

day = "27",

doi = "10.1021/ic061392z",

language = "English",

volume = "45",

pages = "9631--9633",

journal = "Inorganic Chemistry",

issn = "0020-1669",

number = "24",

}

TY - JOUR

T1 - Mechanism of direct molecular oxygen insertion in a palladium(II)-hydride bond

AU - Keith, Jason M.

AU - Muller, Richard P.

AU - Kemp, Richard A.

AU - Goldberg, Karen I.

AU - Goddard, William A.

AU - Oxgaard, Jonas

PY - 2006/11/27

Y1 - 2006/11/27

N2 - The mechanism of the direct insertion of molecular oxygen into a palladium hydride bond has been elucidated using quantum mechanics (B3LYP/LACVP* * with the PBF continuum solvent model). The key step is found to be the abstraction of the hydrogen atom resulting in the formation of a Pd I/HO2 (triplet) radical pair, which then proceeds to form a singlet palladium hydroperoxo species. Potential palladium(0) pathways were explored and were found to be inaccessible. The results are in agreement with recent experimental results and are consistent with our previously predicted mechanism for an analogue system.

AB - The mechanism of the direct insertion of molecular oxygen into a palladium hydride bond has been elucidated using quantum mechanics (B3LYP/LACVP* * with the PBF continuum solvent model). The key step is found to be the abstraction of the hydrogen atom resulting in the formation of a Pd I/HO2 (triplet) radical pair, which then proceeds to form a singlet palladium hydroperoxo species. Potential palladium(0) pathways were explored and were found to be inaccessible. The results are in agreement with recent experimental results and are consistent with our previously predicted mechanism for an analogue system.

UR - https://www.scopus.com/pages/publications/33846146388

U2 - 10.1021/ic061392z

DO - 10.1021/ic061392z

M3 - Article

AN - SCOPUS:33846146388

SN - 0020-1669

VL - 45

SP - 9631

EP - 9633

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 24

ER -

Mechanism of direct molecular oxygen insertion in a palladium(II)-hydride bond

Abstract

Access to Document

Other files and links

Fingerprint

Cite this