P–P Coupling with and without Terminal Metal–Phosphorus Intermediates

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

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Isolation and characterization of a triplet nitrene

Nature Chemistry, Journal Year: 2024, Volume and Issue: 17(1), P. 38 - 43

Published: Nov. 19, 2024

Language: Английский

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Transient Triplet Metallopnictinidenes M–Pn (M = Pd^II, Pt^II; Pn = P, As, Sb): Characterization and Dimerization

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

Published: Jan. 29, 2025

Nitrenes (R–N) have been subject to a large body of experimental and theoretical studies. The fundamental reactivity this important class transient intermediates has attributed their electronic structures, particularly the accessibility triplet vs singlet states. In contrast, structure trends along heavier pnictinidene analogues (R–Pn; Pn = P–Bi) are much less systematically explored. We here report synthesis series metallodipnictenes, {M–Pn═Pn–M} (M PdII, PtII; P, As, Sb, Bi) characterization metallopnictinidene intermediates, {M–Pn} for Sb. Structural, spectroscopic, computational analysis revealed spin ground states metallopnictinidenes with characteristic series. comparison nitrene, pnictinidenes exhibit lower-lying state SOMOs excited states, thus suggesting increased electrophilic reactivity. Furthermore, splitting magnetic microstates is beyond phosphinidenes {M–P} dominated by heavy pnictogen atom induced spin–orbit coupling.

Language: Английский

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A Lead(II) Substituted Triplet Carbene

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(43), P. 29630 - 29636

Published: Oct. 18, 2024

Reaction of the pincer-type ligand L

Language: Английский

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Photoinduced formation of a platina-α-lactone – a carbon dioxide complex of platinum. Insights from femtosecond mid-infrared spectroscopy

Physical Chemistry Chemical Physics, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The oxalate precursor, oxaliplatin, is used to generate a carbon dioxide complex of platinum – species, which can be regarded as metalla-α-lactone.

Language: Английский

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An Open-Shell Fe^IV Nitrido

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

Published: Jan. 19, 2025

We report the photogeneration and characterization of an open-shell, terminal iron nitrido (EmL)Fe(N) using a sterically encumbered dipyrrin ligand environment. The Fe–N distance in solid-state, zero-field 57Fe Mössbauer spectrum, computational analysis are consistent with triplet electronic ground state nitrido. Notably, attenuation multiple bond character through occupying π*Fe–N enables (i) primary C(sp3)–H amination, (ii) H2 cleavage, (iii) aromatic C–C (iv) photocatalytic N-atom transfer reactivity. These modes reactivity have not previously been observed low-spin Fe(N) analogues.

Language: Английский

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Ligand-Dominated Activation of CO₂ and CS₂ by the Putative Nickel Phosphiniminato Intermediates

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(17), P. 7820 - 7827

Published: April 17, 2024

Room-temperature photoactivation of the first- and second-generation PN3P-pincer nickel azido complexes 1a 1b in presence CO2 or CS2 afforded N-bound carbamates, dithiocarbamates, isothiocyanates, providing insights into activation demonstrating how a seemingly small difference ligand structure significantly influences reactivity. Theoretical calculations disclosed that charge phosphorus atom plays critical role determining nitrogen transfer to form plausible phosphiniminato intermediate.

Language: Английский

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C═C Dissociative Imination of Styrenes by a Photogenerated Metallonitrene

JACS Au, Journal Year: 2024, Volume and Issue: 4(9), P. 3421 - 3426

Published: Sept. 3, 2024

Photolysis of a platinum(II) azide complex in the presence styrenes enables C=C double bond cleavage upon dissociative olefin imination to aldimido (Pt

Language: Английский

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Scrutinizing the redox chemistry of group 10 complexes supported by a redox-active bis-phenolate mesoionic carbene

Polyhedron, Journal Year: 2023, Volume and Issue: 250, P. 116786 - 116786

Published: Dec. 13, 2023

We present the synthesis of an isostructural series group 10 mesoionic carbene complexes with general formula [M(MIC)Py] (with M = Ni (1), Pd (2) and Pt (3), Py pyridine MIC bis-phenolate triazolylidene). Their electrochemical properties are investigated, revealing two quasi-reversible oxidations for all compounds, while no reductions observed. Isolation oxidized species has been achieved using either silver triflate or nitrosonium tetrafluoroborate nickel platinum complex yielding corresponding mono-cationic [1]X [3]X (X OTf BF4). For palladium complex, oxidation reactions yielded different products 4 5 in which and/or phenol(oxy) donors were found to be labile compared Pt. Additionally, electron transfer reaction was quite slow short times led isolation unusual heterobimetallic silver-platinum 6. The location redox event investigated EPR spectroscopy computational methods, suggest, that is mostly centered on one phenolate anchors.

Language: Английский

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Ultrafast photogeneration of a metal–organic nitrene from 1,1′-diazidoferrocene

Chemical Science, Journal Year: 2024, Volume and Issue: 15(18), P. 6707 - 6715

Published: Jan. 1, 2024

A bent azide intermediate is key to form 1-azido-1′-nitrenoferrocene from 1,1′-diazidoferrocene, as shown with UV-pump–mid-IR-probe transient absorption spectroscopy and density functional theoryTD-DFT calculations including spin–orbit coupling.

Language: Английский

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