P–P Coupling with and without Terminal Metal–Phosphorus Intermediates DOI Creative Commons
Richard R. Thompson, Matthew T. Figgins,

Duleeka C. Wannipurage

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

Terminal metal–phosphorus (M–P) complexes are of significant contemporary interest as potential platforms for P-atom transfer (PAT) chemistry. Decarbonylation metal–phosphaethynolate (M–PCO) has emerged a general synthetic approach to terminal M–P complexes. that stabilized by strong multiple bonds kinetically persistent and isolable. In the absence stabilization, formation diphosphorus-bridged (i.e., M–P–P–M species) is often interpreted evidence intermediacy reactive, unobserved species. Here, we demonstrate while diphosphorus can arise from reactive species, P–P coupling also proceed directly M–PCO species without Photochemical decarbonylations pincer-supported Ni (II)–PCO complex at 77 K afford spectroscopically observed Ni–P complex, which best described triplet, Ni(II)-metallophosphinidene with two unpaired electrons localized on atomic phosphorus ligand. Thermal annealing this transient results in rapid dimerization corresponding P22–-bridged dinickel complex. Unexpectedly, same be accessed via thermally promoted process light. The analysis reaction kinetics, isotope-labeling studies, computational indicate thermal proceeds noncanonical mechanism avoids intermediates. Together, these represent first observation characterized intermediates not required obtain products. These observations provide critical mechanistic understanding activation modes relevant transfer.

Language: Английский

P–P Coupling with and without Terminal Metal–Phosphorus Intermediates DOI Creative Commons
Richard R. Thompson, Matthew T. Figgins,

Duleeka C. Wannipurage

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

Terminal metal–phosphorus (M–P) complexes are of significant contemporary interest as potential platforms for P-atom transfer (PAT) chemistry. Decarbonylation metal–phosphaethynolate (M–PCO) has emerged a general synthetic approach to terminal M–P complexes. that stabilized by strong multiple bonds kinetically persistent and isolable. In the absence stabilization, formation diphosphorus-bridged (i.e., M–P–P–M species) is often interpreted evidence intermediacy reactive, unobserved species. Here, we demonstrate while diphosphorus can arise from reactive species, P–P coupling also proceed directly M–PCO species without Photochemical decarbonylations pincer-supported Ni (II)–PCO complex at 77 K afford spectroscopically observed Ni–P complex, which best described triplet, Ni(II)-metallophosphinidene with two unpaired electrons localized on atomic phosphorus ligand. Thermal annealing this transient results in rapid dimerization corresponding P22–-bridged dinickel complex. Unexpectedly, same be accessed via thermally promoted process light. The analysis reaction kinetics, isotope-labeling studies, computational indicate thermal proceeds noncanonical mechanism avoids intermediates. Together, these represent first observation characterized intermediates not required obtain products. These observations provide critical mechanistic understanding activation modes relevant transfer.

Language: Английский

Citations

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