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- W2015859892 abstract "Pyridinium-derived N-heterocyclic carbene complexes [(i-BIPY)M(acac)]+[OTf]− (M = Ni (2a), Pd (3a), Pt (4a)) (i-BIPY = N-(2′-pyridyl)-4-tert-butylpyridin-2′-ylidene) are obtained as insoluble microcrystalline powders by cyclometallation of the ligand precursor [i-BIPY-H]+[OTf]− (OTf = trifluormethylsulfonate) to M(acac)2 (acac = acetylacetonate) in chlorobenzene at 160 °C. Consumption of the starting materials in the synthesis of 3a and 4a is complete after 18 h, providing (4a) and (5a) in good yields as analytically pure material after recrystallization. The reaction with Ni(acac)2 is reversible and reaches equilibrium at approximately 75% completion. Removal by distillation of the acetylacetone produced in the cyclometallation drives the reaction to completion furnishing a good yield of pure 6a. Salt metathesis with sodium tetraphenylborate in methanol yields the tetraphenylborate salts (2b–4b) that were used to grow X-ray quality crystals. Analysis of the M–O bond lengths confirms the larger trans-influence of the carbene donor compared with the pyridine donor. Ratios of the M–O(1)/M–O(2) bond lengths suggest that the carbene–metal bond strength follows the order 4b ≈ 3b > 2b. Protonation of 2a–4a with three equivalents of pyridinium hydrochloride produces (i-BIPY)MCl2 in the case of palladium (5) and platinum (6), while in the case of nickel it regenerates the starting [i-BIPY-H]+ and paramagnetic nickel products." @default.
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- W2015859892 title "Pyridinium-derived N-heterocyclic carbene ligands: syntheses, structures and reactivity of N-(2′-pyridyl)pyridin-2-ylidene complexes of nickel(II), palladium(II) and platinum(II)" @default.
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- W2015859892 doi "https://doi.org/10.1016/j.poly.2004.06.021" @default.
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