title: Organo-palladium(II) complexes bearing unsymmetrical N,N,N-pincer ligands: synthesis, structures and oxidatively induced coupling reactions.
abstract: The 2-(2′-aniline)-6-imine-pyridines, 2-(C6H4-2′-NH2)-6-(CMe=NAr)C5H3N (Ar = 4-i-PrC6H4 (HL1a), 2,6-i-Pr2C6H3 (HL1b)), have been synthesised via sequential Stille cross-coupling, deprotection and condensation steps from 6-tributylstannyl-2-(2-methyl-1,3-dioxolan-2-yl)pyridine and 2-bromonitrobenzene. The palladium(II) acetate N,N,N-pincer complexes, [{2-(C6H4-2′-NH)-6-(CMe=NAr)C5H3N}Pd(OAc)] (Ar = 4-i-PrC6H4 (1a), 2,6-i-Pr2C6H3 (1b)), can be prepared by reacting HL1 with Pd(OAc)2 or, in the case of 1a, more conveniently by the template reaction of ketone 2-(C6H4-2′-NH2)-6-(CMe=O)C5H3N, Pd(OAc)2 and 4-isopropylaniline; ready conversion of 1 to their chloride analogues, [{2-(C6H4-2′-NH)-6-(CMe=NAr)C5H3N}PdCl] (Ar = 4-i-PrC6H4 (2a), 2,6-i-Pr2C6H3 (2b)), has been demonstrated. The phenyl-containing complexes, [{2-(C6H4-2′-NH)-6-(CMe=NAr)C5H3N}PdPh] (Ar = 4-i-PrC6H4 (3a), 2,6-i-Pr2C6H3 (3b)), can be obtained by treating HL1 with (PPh3)2PdPh(Br) in the presence of NaH or with regard to 3a, by the salt elimination reaction of 2a with phenyllithium. Reaction of 2a with silver tetrafluoroborate or triflate in the presence of acetonitrile allows access to cationic [{2-(C6H4-2′-NH)-6-(CMe=N(4-i-PrC6H4)C5H3N}Pd(NCMe)][X] (X = BF4 (4), X = O3SCF3 (5)), respectively; the pyridine analogue of 5, [{2-(C6H4-2′-NH)-6-(CMe=N(4-i-PrC6H4)C5H3N}Pd(NC5H5)][O3SCF3] (5′), is also reported. Oxidation of phenyl-containing 3a with one equivalent of 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor™) in acetonitrile at low temperature leads to a new palladium species that slowly decomposes to give 4 and biphenyl; biphenyl formation is also observed upon reaction of 3a with XeF2. However, no such oxidatively induced coupling occurs when using 3b. Single crystal X-ray diffraction studies have been performed on HL1b, 1a, 1b, 2a, 2b, 3a, 3b and 5′.
authors: Department of Chemistry, University of Leicester, University Road, Leicester LE1 7RH, UK. gas8@leicester.ac.uk.
authors: Luka A
authors: LA
authors: Wright
authors: Eric G
authors: EG
authors: Hope
authors: Gregory A
authors: GA
authors: Solan
authors: Warren B
authors: WB
authors: Cross
authors: Kuldip
authors: K
authors: Singh