The first stable base-free terminal uranium phosphinidene metallocene is presented; and its structure and reactivity have been studied in detail and compared to that of the corresponding thorium derivative. Salt metathesis reaction of the methyl iodide uranium metallocene Cp''' U(I)Me (2, Cp'''=η -1,2,4-(Me C) C H ) with Mes*PHK (Mes*=2,4,6-(Me C) C H ) in THF yields the base-free terminal uranium phosphinidene metallocene, Cp''' U=PMes* (3). In addition, density functional theory (DFT) studies suggest substantial 5f orbital contributions to the bonding within the uranium phosphinidene [U]=PAr moiety, which results in a more covalent bonding between the [Cp''' U] and [Mes*P] fragments than that for the related thorium derivative. This difference in bonding besides steric reasons causes different reactivity patterns for both molecules. Therefore, the uranium derivative 3 may act as a Cp''' U(II) synthon releasing the phosphinidene moiety (Mes*P:) when treated with alkynes or a variety of hetero-unsaturated molecules such as imines, thiazoles, ketazines, bipy, organic azides, diazene derivatives, ketones, and carbodiimides.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7756876 | PMC |
| http://dx.doi.org/10.1002/chem.202003465 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Synthesis and reactivity of the uranium phosphinidene metallocene [η-1,3-(MeSi)CH]U(P-2,4,6-PrCH)(OPMe): influence of the coordinated Lewis base.
Dalton Trans
September 2021
Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, Germany.
This paper describes the synthesis and reactivity of [η-1,3-(MeSi)CH]U(P-2,4,6-PrCH)(OPMe) (6) which is accessible from a ligand exchange reaction between [η-1,3-(MeSi)CH]U(P-2,4,6-PrCH)(OPPh) (2) and MePO at ambient temperature. Phosphinidene 6 exhibits no reactivity towards internal alkynes, but readily reacts with various hetero-unsaturated molecules such as isothiocyanates, aldehydes, nitriles, isonitriles, and organic azides, forming uranium sulfido, oxido, imido, and uranaheterocyclic compounds. Nevertheless, with the bidentate -dicyanobenzene -CH(CN) the zwitterionic species [η-1,3-(MeSi)CH]U[NHC(N){CHCP(2,4,6-PrCH)CHPMeO}] (13) is isolated in good yield.
View Article and Find Full Text PDFSystematic Investigation of the Molecular and Electronic Structure of Thorium and Uranium Phosphorus and Arsenic Complexes.
Inorg Chem
July 2021
Department of Chemistry, University of Missouri, 601 S. College Avenue, Columbia 65211, Missouri, United States.
In continuing to examine the interaction of actinide-ligand bonds with soft donor ligands, a comparative investigation with phosphorus and arsenic was conducted. A reaction of (CMe)AnMe, An = Th, U, with 2 equiv of HAsMes, Mes = 2,4,6-MeCH, forms the primary bis(arsenido) complexes, (CMe)An[As(H)Mes]. Both exhibit thermal instability at room temperature, leading to the elimination of H, and the formation of the diarsenido species, (CMe)An(η-AsMes).
View Article and Find Full Text PDFReactivity studies involving a Lewis base supported terminal uranium phosphinidene metallocene [η-1,3-(MeC)CH]U([double bond, length as m-dash]P-2,4,6-PrCH)(OPMe).
Dalton Trans
June 2021
Department of Chemistry, Beijing Normal University, Beijing 100875, China.
The Lewis base supported terminal uranium phosphinidene metallocene [η5-1,3-(Me3C)2C5H3]2U([double bond, length as m-dash]P-2,4,6-iPr3C6H2)(OPMe3) (2) could be isolated from a salt metathesis reaction in toluene at ambient temperature between [η5-1,3-(Me3C)2C5H3]2U(Cl)Me (1) and 2,4,6-iPr3C6H2PHK in the presence of Me3PO, and its structure and reactivity were probed in detail. No reaction of 2 with internal alkynes was observed, but it reacts in the presence of various heterounsaturated molecules such as CS2, isothiocyanates, aldehydes, imines, diazenes, carbodiimides, nitriles, isonitriles, diazoalkane, and organic azides, forming carbodithioates, sulfidos, oxidos, metallaheterocycles, and imido complexes, in good yields. Moreover, on reaction with the diazoalkane derivative Me3SiCHN2 the pseudophosphinimido uranium(iii) complex [η5-1,3-(Me3C)2C5H3]2U(N[double bond, length as m-dash]P-2,4,6-iPr3C6H2)(OPMe3) (20) can be isolated in good yield.
View Article and Find Full Text PDFUranium versus Thorium: Synthesis and Reactivity of [η -1,2,4-(Me C) C H ] U[η -C Ph ].
Chemistry
April 2021
Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106, Braunschweig, Germany.
The synthesis, electronic structure, and reactivity of a uranium metallacyclopropene were comprehensively studied. Addition of diphenylacetylene (PhC≡CPh) to the uranium phosphinidene metallocene [η -1,2,4-(Me C) C H ] U=P-2,4,6-tBu C H (1) yields the stable uranium metallacyclopropene, [η -1,2,4-(Me C) C H ] U[η -C Ph ] (2). Based on density functional theory (DFT) results the 5f orbital contributions to the bonding within the metallacyclopropene U-(η -C=C) moiety increases significantly compared to the related Th compound [η -1,2,4-(Me C) C H ] Th[η -C Ph ], which also results in more covalent bonds between the [η -1,2,4-(Me C) C H ] U and [η -C Ph ] fragments.
View Article and Find Full Text PDFA Lewis Base Supported Terminal Uranium Phosphinidene Metallocene.
Inorg Chem
October 2020
Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, Germany.
A Lewis base supported terminal uranium phosphinidene, [η-1,3-(MeC)CH]U(═P-2,4,6-BuCH)(OPMe) (), is isolated from the reaction of the uranium methyl chloride [η-1,3-(MeC)CH]U(Cl)Me () with 2,4,6-(MeC)CHPHK in toluene in the presence of MePO. Moreover, the reactivity of uranium phospinidene toward a series of small molecules was comprehensively explored. While no reactivity of with internal alkynes is observed attributed to steric hindrance, it readily reacts in good yields with various small molecules including isothiocyanates, aldehydes, imines, diazenes, carbodiimides, nitriles, isonitriles, and organic azides, yielding uranium sulfidos, oxidos, metallaheterocycles, and imido complexes.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!