Direct arylation mediated by palladium complexes with rigid Phosphine-Functionalized N-Heterocyclic carbenes

Ho Chien-Chang, Sandipan Chatterjee, Wu Tzu-Liang, Chan Kai-Ting, Chang Yu-Wei, Hsiao Tsun-Hung, Hon Man Lee

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Abstract

New phosphine-functionalized N-heterocyclic carbene ligand precursors (L1H I and L2H I) were prepared. The former compound contains a PPh2 moiety, whereas the latter one has a more electrondonating PCy2 group. A reaction of L1H ⋯ I with PdCl 2 in the presence of base afforded the complex PdL1ClI. An interconversion process between the two structural isomers of PdL 1ClI was observed by variable-temperature NMR. The coalescence temperature (Tc) is at 368 K with the free energy of activation (δG±) found to be 68.9 kJ mol-1. A similar reaction of L2H I with PdCl2 produced a mixture of PdL2ClI, PdL 2Cl2, and PdL2I2. Unlike PdL1ClI, PdL 2ClI undergoes a much faster exchange between the two structural isomers. Pure PdLI2 (L = L1 and L2) can be obtained by adding NaI in the reaction mixture to facilitate ligand exchange. [PdL(CH3C=N2](BF4)2 were also prepared straightforwardly by salt metathesis reactions. In total, seven new palladium complexes of L were structurally characterized, and in each of these structures an anagostic interaction exists between the palladium center and one of the diastereotopic methylene protons. The interaction also exists in solution, as evidenced by the downfield NMR shift of the proton. The new complexes PdLI2 and [PdL(CH3C=N)2](BF4) 2 show mediocre activities in benchmark Suzuki coupling reactions under conventional and microwave heating. They are, however, highly promising in mediating direct arylation of phenyl halides and diphenylacetylene, affording 9-benzylidene-9H-fluorene in good yields.

Original languageEnglish
Pages (from-to)2837-2847
Number of pages11
JournalOrganometallics
Volume28
Issue number9
DOIs
Publication statusPublished - 2009 May 11

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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    Chien-Chang, H., Chatterjee, S., Tzu-Liang, W., Kai-Ting, C., Yu-Wei, C., Tsun-Hung, H., & Lee, H. M. (2009). Direct arylation mediated by palladium complexes with rigid Phosphine-Functionalized N-Heterocyclic carbenes. Organometallics, 28(9), 2837-2847. https://doi.org/10.1021/om900112y