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Reactivity of a Dinuclear Pd(I) Complex [Pd(2)(μ-PPh(2))(μ(2)-OAc)(PPh(3))(2)] with PPh(3): Implications for Cross-Coupling Catalysis Using the Ubiquitous Pd(OAc)(2)/nPPh(3) Catalyst System
[Image: see text] [Pd(I)(2)(μ-PPh(2))(μ(2)-OAc)(PPh(3))(2)] is the reduction product of Pd(II)(OAc)(2)(PPh(3))(2), generated by reaction of ‘Pd(OAc)(2)’ with two equivalents of PPh(3). Here, we report that the reaction of [Pd(I)(2)(μ-PPh(2))(μ(2)-OAc)(PPh(3))(2)] with PPh(3) results in a nuanced dis...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2021
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8441971/ https://www.ncbi.nlm.nih.gov/pubmed/34539028 http://dx.doi.org/10.1021/acs.organomet.1c00347 |
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author | Scott, Neil W. J. Ford, Mark J. Husbands, David R. Whitwood, Adrian C. Fairlamb, Ian J. S. |
author_facet | Scott, Neil W. J. Ford, Mark J. Husbands, David R. Whitwood, Adrian C. Fairlamb, Ian J. S. |
author_sort | Scott, Neil W. J. |
collection | PubMed |
description | [Image: see text] [Pd(I)(2)(μ-PPh(2))(μ(2)-OAc)(PPh(3))(2)] is the reduction product of Pd(II)(OAc)(2)(PPh(3))(2), generated by reaction of ‘Pd(OAc)(2)’ with two equivalents of PPh(3). Here, we report that the reaction of [Pd(I)(2)(μ-PPh(2))(μ(2)-OAc)(PPh(3))(2)] with PPh(3) results in a nuanced disproportionation reaction, forming [Pd(0)(PPh(3))(3)] and a phosphinito-bridged Pd(I)-dinuclear complex, namely [Pd(I)(2)(μ-PPh(2)){κ(2)-P,O-μ-P(O)Ph(2)}(κ-PPh(3))(2)]. The latter complex is proposed to form by abstraction of an oxygen atom from an acetate ligand at Pd. A mechanism for the formal reduction of a putative Pd(II) disproportionation species to the observed Pd(I) complex is postulated. Upon reaction of the mixture of [Pd(0)(PPh)(3)] and [Pd(I)(2)(μ-PPh(2)){κ(2)-P,O-μ-P(O)Ph(2)}(κ-PPh(3))(2)] with 2-bromopyridine, the former Pd(0) complex undergoes a fast oxidative addition reaction, while the latter dinuclear Pd(I) complex converts slowly to a tripalladium cluster, of the type [Pd(3)(μ-X)(μ-PPh(2))(2)(PPh(3))(3)]X, with an overall 4/3 oxidation state per Pd. Our findings reveal complexity associated with the precatalyst activation step for the ubiquitous ‘Pd(OAc)(2)’/nPPh(3) catalyst system, with implications for cross-coupling catalysis. |
format | Online Article Text |
id | pubmed-8441971 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-84419712021-09-15 Reactivity of a Dinuclear Pd(I) Complex [Pd(2)(μ-PPh(2))(μ(2)-OAc)(PPh(3))(2)] with PPh(3): Implications for Cross-Coupling Catalysis Using the Ubiquitous Pd(OAc)(2)/nPPh(3) Catalyst System Scott, Neil W. J. Ford, Mark J. Husbands, David R. Whitwood, Adrian C. Fairlamb, Ian J. S. Organometallics [Image: see text] [Pd(I)(2)(μ-PPh(2))(μ(2)-OAc)(PPh(3))(2)] is the reduction product of Pd(II)(OAc)(2)(PPh(3))(2), generated by reaction of ‘Pd(OAc)(2)’ with two equivalents of PPh(3). Here, we report that the reaction of [Pd(I)(2)(μ-PPh(2))(μ(2)-OAc)(PPh(3))(2)] with PPh(3) results in a nuanced disproportionation reaction, forming [Pd(0)(PPh(3))(3)] and a phosphinito-bridged Pd(I)-dinuclear complex, namely [Pd(I)(2)(μ-PPh(2)){κ(2)-P,O-μ-P(O)Ph(2)}(κ-PPh(3))(2)]. The latter complex is proposed to form by abstraction of an oxygen atom from an acetate ligand at Pd. A mechanism for the formal reduction of a putative Pd(II) disproportionation species to the observed Pd(I) complex is postulated. Upon reaction of the mixture of [Pd(0)(PPh)(3)] and [Pd(I)(2)(μ-PPh(2)){κ(2)-P,O-μ-P(O)Ph(2)}(κ-PPh(3))(2)] with 2-bromopyridine, the former Pd(0) complex undergoes a fast oxidative addition reaction, while the latter dinuclear Pd(I) complex converts slowly to a tripalladium cluster, of the type [Pd(3)(μ-X)(μ-PPh(2))(2)(PPh(3))(3)]X, with an overall 4/3 oxidation state per Pd. Our findings reveal complexity associated with the precatalyst activation step for the ubiquitous ‘Pd(OAc)(2)’/nPPh(3) catalyst system, with implications for cross-coupling catalysis. American Chemical Society 2021-08-19 2021-09-13 /pmc/articles/PMC8441971/ /pubmed/34539028 http://dx.doi.org/10.1021/acs.organomet.1c00347 Text en © 2021 American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Scott, Neil W. J. Ford, Mark J. Husbands, David R. Whitwood, Adrian C. Fairlamb, Ian J. S. Reactivity of a Dinuclear Pd(I) Complex [Pd(2)(μ-PPh(2))(μ(2)-OAc)(PPh(3))(2)] with PPh(3): Implications for Cross-Coupling Catalysis Using the Ubiquitous Pd(OAc)(2)/nPPh(3) Catalyst System |
title | Reactivity of a Dinuclear Pd(I) Complex [Pd(2)(μ-PPh(2))(μ(2)-OAc)(PPh(3))(2)] with PPh(3): Implications for Cross-Coupling
Catalysis Using the Ubiquitous Pd(OAc)(2)/nPPh(3) Catalyst System |
title_full | Reactivity of a Dinuclear Pd(I) Complex [Pd(2)(μ-PPh(2))(μ(2)-OAc)(PPh(3))(2)] with PPh(3): Implications for Cross-Coupling
Catalysis Using the Ubiquitous Pd(OAc)(2)/nPPh(3) Catalyst System |
title_fullStr | Reactivity of a Dinuclear Pd(I) Complex [Pd(2)(μ-PPh(2))(μ(2)-OAc)(PPh(3))(2)] with PPh(3): Implications for Cross-Coupling
Catalysis Using the Ubiquitous Pd(OAc)(2)/nPPh(3) Catalyst System |
title_full_unstemmed | Reactivity of a Dinuclear Pd(I) Complex [Pd(2)(μ-PPh(2))(μ(2)-OAc)(PPh(3))(2)] with PPh(3): Implications for Cross-Coupling
Catalysis Using the Ubiquitous Pd(OAc)(2)/nPPh(3) Catalyst System |
title_short | Reactivity of a Dinuclear Pd(I) Complex [Pd(2)(μ-PPh(2))(μ(2)-OAc)(PPh(3))(2)] with PPh(3): Implications for Cross-Coupling
Catalysis Using the Ubiquitous Pd(OAc)(2)/nPPh(3) Catalyst System |
title_sort | reactivity of a dinuclear pd(i) complex [pd(2)(μ-pph(2))(μ(2)-oac)(pph(3))(2)] with pph(3): implications for cross-coupling
catalysis using the ubiquitous pd(oac)(2)/npph(3) catalyst system |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8441971/ https://www.ncbi.nlm.nih.gov/pubmed/34539028 http://dx.doi.org/10.1021/acs.organomet.1c00347 |
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