Intramolecular Nitrile C–H Bond Activation in Nickel NHC Complexes: A Route to New Nickelacycles

Abstract

Cyclopentadienyl N-heterocyclic carbene (NHC) nickel complexes of general formula [Ni(NHC)XCp] (NHC = 1-(propylnitrile)-3-methylimidazol-2-ylidene, 1-(2,4,6-trimethylphenyl)-3-(butylnitrile)imidazol-2-ylidene, 1-(2,4,6-trimethylphenyl)-3-(pentylnitrile)imidazol-2-ylidene, 1-(2,4,6-trimethylphenyl)-3-(hexylnitrile)imidazol-2-ylidene; X = Cl, Br, I; Cp = η5-C5H5), which bear an alkylnitrile side chain attached to one of the nitrogen atoms of the NHC ring, were prepared by the direct reaction of nickelocene with the corresponding imidazolium salts (NHC·HX). The new complexes [Ni{Me-NHC-(CH2)2CN}ICp] (1a), [Ni{Mes-NHC-(CH2)3CN}ClCp] (1b), [Ni{Mes-NHC-(CH2)4CN}ICp] (1c), and [Ni{Mes-NHC-(CH2)5CN}BrCp] (1d) were obtained in good yields and were fully characterized by standard spectroscopic techniques and elemental analyses and, in the cases of 1a,b, by single-crystal X-ray crystallography. Structural studies established their two-legged piano-stool geometry. The cationic derivatives [Ni{Mes-NHC-(CH2)nCN}(NCMe)Cp]+ (2b–d; n = 3–5) were prepared from the reaction of their neutral homologues 1b−d with KPF6 in acetonitrile at room temperature. Upon treatment of the neutral complexes 1 or of the cationic compounds 2 with KO-t-Bu, a C–H bond α to the nitrile group in each molecule underwent a base-promoted C–H activation and the new nickelacyclic complexes [Ni{Me-NHC-CH2CH(CN)}Cp] (3a) and [Ni{Mes-NHC-(CH2)nCH(CN)}Cp] (3b–d; n = 2–4) were obtained. All of these metallacycles contain Ni–C σ-bonds, and their synthesis generated a new asymmetric carbon center. The cyclic complexes 3 were fully characterized by 1H and 13C NMR spectroscopy, IR spectroscopy, and elemental analyses. The structures of complexes 3b and 3d, which contain six- and eight-membered metallacyclic rings, respectively, were determined by single-crystal X-ray diffraction studies. DFT studies, carried out to probe the mechanism of these cyclonickelation reactions, indicated that the mechanism of formation of these nickelacycles was similar to that observed for the formation of cyanomethyl ligands from coordinated acetonitrile. Nevertheless, the base deprotonation of an α-C–H ligand in a side arm, while thermodynamically comparable to that of a simultaneously coordinated acetonitrile ligand, is kinetically favored, and this leads to the formation of nickelacycles rather than cyanomethyl complexes in the case of the base-assisted activation of the cationic complexes 2.