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Phosphorus-Atom Transfer from Phosphaethynolate to an Alkylidyne

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Title
Phosphorus-Atom Transfer from Phosphaethynolate to an Alkylidyne
Author(s)
Jafari, Mehrafshan G.; Yerin Park; Bimal Pudasaini; Kurogi, Takashi; Carroll, Patrick J.; Kaphan, David M.; Kropf, Jeremy; Delferro, Massimiliano; Mu-Hyun Baik; Mindiola, Daniel J.
Publication Date
2021-11
Journal
Angewandte Chemie - International Edition, v.60, no.46, pp.24411 - 24417
Publisher
John Wiley and Sons Inc
Abstract
© 2021 Wiley-VCH GmbH A low-spin and mononuclear vanadium complex, (Menacnac)V(CO)(η2-P≡CtBu) (2) (Menacnac−=[ArNC(CH3)]2CH, Ar=2,6-iPr2C6H3), was prepared upon treatment of the vanadium neopentylidyne complex (Menacnac)V≡CtBu(OTf) (1) with Na(OCP)(diox)2.5 (diox=1,4-dioxane), while the isoelectronic ate-complex [Na(15-crown-5)]{([ArNC(CH2)]CH[C(CH3)NAr])V(CO)(η2-P≡CtBu)} (4), was obtained via the reaction of Na(OCP)(diox)2.5 and ([ArNC(CH2)]CH[C(CH3)NAr])V≡CtBu(OEt2) (3) in the presence of crown-ether. Computational studies suggest that the P-atom transfer proceeds by [2+2]-cycloaddition of the P≡C bond across the V≡CtBu moiety, followed by a reductive decarbonylation to form the V−C≡O linkage. The nature of the electronic ground state in diamagnetic complexes, 2 and 4, was further investigated both theoretically and experimentally, using a combination of density functional theory (DFT) calculations, UV/Vis and NMR spectroscopies, cyclic voltammetry, X-ray absorption spectroscopy (XAS) measurements, and comparison of salient bond metrics derived from X-ray single-crystal structural characterization. In combination, these data are consistent with a low-valent vanadium ion in complexes 2 and 4. This study represents the first example of a metathesis reaction between the P-atom of [PCO]− and an alkylidyne ligand.
URI
https://pr.ibs.re.kr/handle/8788114/10676
DOI
10.1002/anie.202107475
ISSN
1433-7851
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > 1. Journal Papers (저널논문)
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