FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2092116864> ?p ?o ?g. }

• W2092116864 endingPage "5025" @default.
• W2092116864 startingPage "5010" @default.
• W2092116864 abstract "We have investigated both the chemical reduction of (BDI)NbV imido complexes (BDI = HC[C(Me)NAr]2; Ar = 2,6-iPr2-C6H3) to the formal Nb(III) oxidation state and the ability of these Nb(III) complexes to behave as two-electron reductants. The reduction of the Nb(V) species was found to depend heavily on the nature of available supporting ligands, but the chemistry of the reduced compounds proceeded cleanly with a number of unsaturated organic reagents. Accordingly, novel Nb(V) bis(imido) complexes supported by the monoazabutadiene (mad) ligand (mad)Nb(NtBu)(NAr)(L′) (L′ = py, thf) were formed by either KC8 reduction of (BDI)Nb(NtBu)Cl2(py) in the absence of strong π-acids or by H2 reduction of the Nb(V) dimethyl complex (BDI)Nb(NtBu)Me2 in THF. These products are likely formed though an intramolecular 2e reductive C−N bond cleavage, as has been observed previously for related group 4 systems, suggesting that transient Nb(III) intermediates were present in both cases. In the presence of 1,2-bis(dimethylphosphino)ethane (dmpe), KC8 reduction of (BDI)Nb(NtBu)Cl2(py) was arrested at the Nb(IV) oxidation state to give (BDI)Nb(NtBu)Cl(dmpe), which was characterized by solution-state EPR spectroscopy as a Nb-centered paramagnet with strong coupling to the two equivalent phosphorus nuclei (Aiso{93Nb} = 120.5 × 10−4 cm−1, Aiso{31P} = 31.0 × 10−4 cm−1, giso = 1.9815). When strong π-acids were used to intercept the thermally unstable Nb(III) complex (BDI)Nb(NtBu)(py) prior to reductive cleavage of the ligand C−N bond, the thermally stable Nb(III) species (BDI)Nb(NtBu)(CX)2(L′′) (X = O, L′′= py; X = NXyl, L′′ = CNXyl; Xyl =2,6-Me2-C6H3) were obtained in good yields. The Nb(III) complexes (BDI)Nb(NtBu)py, (BDI)Nb(NtBu)(CO)2(py), and (BDI)Nb(NtBu)(CO)2 were subsequently investigated for their ability to serve as two-electron reducing reagents for both metal−ligand multiple bond formation and for the reduction of organic π-systems. The reduction of mesityl azide by (BDI)Nb(NtBu)(py) and diphenyl sulfoxide by (BDI)Nb(NtBu)(CO)2 led to the monomeric bis(imido) and dimeric oxo complexes (BDI)Nb(NtBu)(NMes)(py) and [(BDI)Nb(NtBu)]2(μ2-O)2, respectively. MeLi addition to (BDI)Nb(NtBu)(CO)2(py) resulted in the formation of a Nb acylate via methide addition to one of the carbonyl carbons. The acylate product was revealed to have a short Nb−Cacylate bond distance (2.059(4) Å), consistent with multiple Nb−C bond character resulting from Nb(III) back-bonding into the acylate carbon. The interaction of (BDI)Nb(NtBu)(CO)2 with 2 equiv of 4,4′-dichlorobenzophenone resulted in the clean, quantitative formation of the corresponding pinacol coupling product, but introduction of the ketone in 1:1 molar ratios resulted in mixtures of the pinacol product and the starting material, suggesting that ketone coordination to the Nb(III) complex may be reversible. In a related manner, addition of 1-phenyl-1-propyne to (BDI)Nb(NtBu)(CO)2 formed a thermally unstable 1:1 Nb/alkyne complex, as characterized by NMR and IR spectroscopy; reaction of this species with HCl/MeOH yielded a 2:1 mixture of 1-phenyl-1-propene and the free alkyne, suggesting a high degree of covalency in the Nb−C bonds." @default.
• W2092116864 created "2016-06-24" @default.
• W2092116864 creator A5018749169 @default.
• W2092116864 creator A5023860166 @default.
• W2092116864 creator A5047518475 @default.
• W2092116864 date "2010-07-13" @default.
• W2092116864 modified "2023-10-17" @default.
• W2092116864 title "Synthesis, Characterization, and Reactions of Isolable (β-Diketiminato)niobium(III) Imido Complexes" @default.
• W2092116864 cites W1529121934 @default.
• W2092116864 cites W1954084135 @default.
• W2092116864 cites W1963491087 @default.
• W2092116864 cites W1968930748 @default.
• W2092116864 cites W1973415300 @default.
• W2092116864 cites W1975557068 @default.
• W2092116864 cites W1975848173 @default.
• W2092116864 cites W1980693907 @default.
• W2092116864 cites W1980911676 @default.
• W2092116864 cites W1981730841 @default.
• W2092116864 cites W1982472536 @default.
• W2092116864 cites W1984590110 @default.
• W2092116864 cites W1985415489 @default.
• W2092116864 cites W1985416107 @default.
• W2092116864 cites W1991836245 @default.
• W2092116864 cites W1991980693 @default.
• W2092116864 cites W1994358660 @default.
• W2092116864 cites W2002788226 @default.
• W2092116864 cites W2002848990 @default.
• W2092116864 cites W2007390940 @default.
• W2092116864 cites W2007862348 @default.
• W2092116864 cites W2013498890 @default.
• W2092116864 cites W2014289079 @default.
• W2092116864 cites W2018061964 @default.
• W2092116864 cites W2021518855 @default.
• W2092116864 cites W2021630604 @default.
• W2092116864 cites W2022415624 @default.
• W2092116864 cites W2023478234 @default.
• W2092116864 cites W2026228805 @default.
• W2092116864 cites W2026838218 @default.
• W2092116864 cites W2029658403 @default.
• W2092116864 cites W2032207589 @default.
• W2092116864 cites W2032449459 @default.
• W2092116864 cites W2036043284 @default.
• W2092116864 cites W2041190978 @default.
• W2092116864 cites W2042474107 @default.
• W2092116864 cites W2042899791 @default.
• W2092116864 cites W2051769797 @default.
• W2092116864 cites W2055114774 @default.
• W2092116864 cites W2058691315 @default.
• W2092116864 cites W2059020082 @default.
• W2092116864 cites W2062210247 @default.
• W2092116864 cites W2062975057 @default.
• W2092116864 cites W2068099826 @default.
• W2092116864 cites W2069279071 @default.
• W2092116864 cites W2071956014 @default.
• W2092116864 cites W2072301212 @default.
• W2092116864 cites W2076191524 @default.
• W2092116864 cites W2079262904 @default.
• W2092116864 cites W2082927131 @default.
• W2092116864 cites W2087566204 @default.
• W2092116864 cites W2087853089 @default.
• W2092116864 cites W2087892696 @default.
• W2092116864 cites W2088787961 @default.
• W2092116864 cites W2089622097 @default.
• W2092116864 cites W2092831810 @default.
• W2092116864 cites W2093433105 @default.
• W2092116864 cites W2095141346 @default.
• W2092116864 cites W2097713654 @default.
• W2092116864 cites W2105249240 @default.
• W2092116864 cites W2121237359 @default.
• W2092116864 cites W2136575878 @default.
• W2092116864 cites W2149295256 @default.
• W2092116864 cites W2604437599 @default.
• W2092116864 cites W2949149631 @default.
• W2092116864 cites W2951229345 @default.
• W2092116864 cites W3005460847 @default.
• W2092116864 doi "https://doi.org/10.1021/om1002528" @default.
• W2092116864 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/2992439" @default.
• W2092116864 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/21116450" @default.
• W2092116864 hasPublicationYear "2010" @default.
• W2092116864 type Work @default.
• W2092116864 sameAs 2092116864 @default.
• W2092116864 citedByCount "56" @default.
• W2092116864 countsByYear W20921168642012 @default.
• W2092116864 countsByYear W20921168642013 @default.
• W2092116864 countsByYear W20921168642014 @default.
• W2092116864 countsByYear W20921168642015 @default.
• W2092116864 countsByYear W20921168642016 @default.
• W2092116864 countsByYear W20921168642017 @default.
• W2092116864 countsByYear W20921168642018 @default.
• W2092116864 countsByYear W20921168642019 @default.
• W2092116864 countsByYear W20921168642020 @default.
• W2092116864 countsByYear W20921168642021 @default.
• W2092116864 countsByYear W20921168642022 @default.
• W2092116864 countsByYear W20921168642023 @default.
• W2092116864 crossrefType "journal-article" @default.
• W2092116864 hasAuthorship W2092116864A5018749169 @default.
• W2092116864 hasAuthorship W2092116864A5023860166 @default.
• W2092116864 hasAuthorship W2092116864A5047518475 @default.

• next