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Ru -Acylimido Intermediate in [Ru (Por)Cl ]-Catalyzed C-N Bond Formation: Spectroscopic Characterization, Reactivity, and Catalytic Reactions.
Angew Chem Int Ed Engl
August 2021
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong SAR, China.
Metal-catalyzed C-N bond formation reactions via acylnitrene transfer have recently attracted much attention, but direct detection of the proposed acylnitrenoid/acylimido M(NCOR) (R=aryl or alkyl) species in these reactions poses a formidable challenge. Herein, we report on Ru(NCOR) intermediates in C-N bond formation catalyzed by [Ru (Por)Cl ]/N COR, a catalytic method applicable to aziridine/oxazoline formation from alkenes, amination of substituted indoles, α-amino ketone formation from silyl enol ethers, amination of C(sp )-H bonds, and functionalization of natural products and carbohydrate derivatives (up to 99 % yield). Experimental studies, including HR-ESI-MS and EPR measurements, coupled with DFT calculations, lend evidence for the formulation of the Ru(NCOR) acylnitrenoids as a Ru -imido species.
View Article and Find Full Text PDFA nitridoniobium(V) reagent that effects acid chloride to organic nitrile conversion: synthesis via heterodinuclear (Nb/Mo) dinitrogen cleavage, mechanistic insights, and recycling.
J Am Chem Soc
January 2006
Massachusetts Institute of Technology, Room 2-227, 77 Massachusetts Avenue, Cambridge Massachusetts 02139, USA.
The transformation of acid chlorides (RC(O)Cl) to organic nitriles (RC[triple bond]N) by the terminal niobium nitride anion [N[triple bond]Nb(N[Np]Ar)3]- ([1a-N]-, where Np = neopentyl and Ar = 3,5-Me2C6H3) via isovalent N for O(Cl) metathetical exchange is presented. Nitrido anion [1a-N]- is obtained in a heterodinuclear N2 scission reaction employing the molybdenum trisamide system, Mo(N[R]Ar)3 (R = t-Bu, 2a; R = Np, 2b), as a reaction partner. Reductive scission of the heterodinuclear bridging N2 complexes, (Ar[R]N)3Mo-(mu-N2)Nb(N[Np]Ar)3 (R = t-Bu, 3b; R = Np, 3c) with sodium amalgam provides 1 equiv each of the salt Na[1a-N] and neutral N[triple bond]Mo(N[R]Ar)3 (R = t-Bu, 2a-N; R = Np, 2b-N).
View Article and Find Full Text PDFOrganic nitriles from acid chlorides: an isovalent N for (O)CL exchange reaction mediated by a tungsten nitride complex.
J Am Chem Soc
June 2004
Department of Chemistry, Massachusetts Institutes of Technology, 77 Massachusetts Avenue, Room 2-227, Cambridge, Massachusetts 02139-4307, USA.
Nitride NW(N[i-Pr]Ar)3 (1, Ar = 3,5-C6H3Me2) was synthesized in two steps from known NW(O-t-Bu)3 (41% overall yield). Complex 1 is the tungsten congener of NMo(N[i-Pr]Ar)3, a known molecule that has been synthesized using N2 as the nitrido nitrogen source, but which undergoes no reaction with pivaloyl chloride. Compound 1 undergoes metathesis with pivaloyl chloride at 25 degrees C to form the corresponding nitrile in 97% yield.
View Article and Find Full Text PDFReactions of Nitridorhenium(V) and -Osmium(VI) Complexes with Acylating Agents.
Inorg Chem
June 1999
Departments of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, and The University of Hong Kong, Pokfulam Road, Hong Kong.
Interaction of Re(N)L(2) [L = N(PSPh(2))(2)] 1 with (CF(3)CO)(2)O or RCOCl afforded air-sensitive acylimido-Re(V) complexes trans-Re[NC(O)CF(3)](OCOCF(3))L(2) 2 or trans-Re[NC(O)R]ClL(2) (R = CCl(2)H 3, CClH(2) 4, CH(3) 5), respectively. Treatment of 1 with (CX(3)CO)(2)O followed by recrystallization from CH(2)Cl(2)/hexane in air led to the formation of the corresponding parent imido complexes trans-Re(NH)(OCOCX(3))L(2) (X = F 6, Cl 7). The structure of 7 has been characterized by X-ray crystallography.
View Article and Find Full Text PDFAcylimido Complexes of Tungsten(IV) Formed by Oxygen Atom Transfer to Nitrile-kappa(2)N,C Complexes.
Inorg Chem
February 1998
School of Chemistry, University of Melbourne, Parkville, Victoria 3052, Australia.
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