In:
Angewandte Chemie, Wiley, Vol. 133, No. 46 ( 2021-11-08), p. 24616-24622
Abstract:
A low‐spin and mononuclear vanadium complex, ( Me nacnac)V(CO)(η 2 ‐P≡C t Bu) ( 2 ) ( Me nacnac − =[ArNC(CH 3 )] 2 CH, Ar=2,6‐ i Pr 2 C 6 H 3 ), was prepared upon treatment of the vanadium neopentylidyne complex ( Me nacnac)V≡C t Bu(OTf) ( 1 ) with Na(OCP)(diox) 2.5 (diox=1,4‐dioxane), while the isoelectronic ate‐complex [Na(15‐crown‐5)]{([ArNC(CH 2 )]CH[C(CH 3 )NAr])V(CO)(η 2 ‐P≡C t Bu)} ( 4 ), was obtained via the reaction of Na(OCP)(diox) 2.5 and ([ArNC(CH 2 )]CH[C(CH 3 )NAr])V≡C t Bu(OEt 2 ) ( 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≡C t Bu 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.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v133.46
DOI:
10.1002/ange.202107475
Language:
English
Publisher:
Wiley
Publication Date:
2021
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