1,3-Dipolar Cycloaddition of Nitrones to Gold(III)-Bound Isocyanides

Tatyana B. Anisimova, Mikhail A. Kinzhalov, Maxim L. Kuznetsov, M. Fátima C. Guedes Da Silva, Andrey A. Zolotarev, Vadim Yu Kukushkin, Armando J.L. Pombeiro, Konstantin V. Luzyanin

Research output

3 Citations (Scopus)

Abstract

Treatment of gold(III)-isocyanides [AuCl3(CNR1)] (R1 = Xyl 1, Cy 2, But 3) with an equimolar amount of 5,5-dimethyl-1-pyrroline-N-oxide (4) in CH2Cl2 at -74 °C leads to the generation of the heterocyclic aminocarbene species [AuCl3{C(ONaCMe2CH2CH2CbH)=NeR1}(Na-Cb)(Cb-Ne)] 8 (for R1 = But) or gold(III) complexes cis-[AuCl2{Na(CMe2CH2CH2CbNeR1)Cd=O}(Na=Cb)(Ne-Cd)] 9 and 10 (for R1 = Xyl and Cy) in good isolated yields (75-87%). DFT calculations show that deprotonation of the endocyclic CH group in the carbene ligand leads to spontaneous N-O bond cleavage, and acidity of this group is a factor controlling the different chemical behavior of 1-3 depending on the nature of substituent R1. The reaction of equimolar amounts of the aldonitrone p-TolCH=N+(Me)O- (5) or the ketonitrones Ph2C=N+(R2)O- (R2 = Ph 6, CH2Ph 7) with 1-3 in CD2Cl2 at -70 °C in air (or under N2) revealed the formation of the carbene complexes [AuCl3{C(ONMeCaH-p-Tol)=NbR1}(Ca-Nb)] (R1 = Cy 11, Xyl 12, But 13), [AuCl3{C(ONPhCaPh2)=NbR1}(Ca-Nb)] (R1 = Cy 14, But 15), or [AuCl3{C(ON(CH2Ph)CaPh2)=NbR1}(Ca-Nb)] (R1 = Cy 16, Xyl 17), as studied by 1H NMR. The reaction of 6 with 1 and of 7 with 3 did not furnish carbene products. Compounds 8-10 were characterized by ESI-MS, IR, 1D (1H, 13C{H}) and 2D (1H,1H-COSY, 1H,13C-HSQC, 1H,13C-HMBC) NMR spectroscopic techniques, and, only for 8, elemental analyses (C, H, N), while compounds 11-17 were characterized by 1D (1H, 13C{H}) and 2D (1H,13C-HSQC) NMR. Structures of compounds 8, 9, and 13 were additionally established by single-crystal X-ray diffraction.

Original languageEnglish
Pages (from-to)3569-3576
Number of pages8
JournalOrganometallics
Volume35
Issue number20
DOIs
Publication statusPublished - 24 Oct 2016

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Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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