Zirconium complexes with versatile β-diketiminate ligands: Synthesis, structure, and ethylene polymerization

Coordination modes in zirconium β-diketiminate complexes

“…The N1, N2, C1, C2 fragment remains essentially planar with twist angles below 10°. The latter group (3,4,(9)(10)(11)(12) shows a distorted ligand mean plane with twist angles above 15°, significant differences in Zr-C2/4 distances (>0.2 Å), in Zr-C2/4-C1/5 angles (>25°) and increased C-N-C2/ 4-C1/5 torsion angles (>15°).…”

“…In mono- [2][3][4][5][6][7][8][9] and bis(diketiminate) complexes of zirconium [4,6,7,10], as well as in complexes with the related iminomethylaniline [11,12] or azaallylpyridine ligands [13,14], the ligand is bound via the two nitrogen lone pairs with the metal found in the ligand mean plane (Scheme 1, A). Steric crowding around the metal center, in particular with sterically demanding substituents on nitrogen, results in a displacement of the metal out of the ligand mean plane (Scheme 1, B) [1,3].…”

A Tetradentate β‐Diiminato Ligand Containing Phenolate Substituents: Flexivalent Coordination to MnIII, CoIII, NiII, and CuII

“…[1][2][3][4] The resulting complexes display interesting structural features, which may give the compounds important catalytic activity, for example, in the polymerization of lactide, [5,6] isoprene, [7] ethylene, [8][9][10] and propylene, [11] the copolymerization of epoxide and CO 2 , [12] and also in the oxidation of alkanes [13] and cyclohexene. [1][2][3][4] The resulting complexes display interesting structural features, which may give the compounds important catalytic activity, for example, in the polymerization of lactide, [5,6] isoprene, [7] ethylene, [8][9][10] and propylene, [11] the copolymerization of epoxide and CO 2 , [12] and also in the oxidation of alkanes [13] and cyclohexene.…”

“…, HCN),9.42 (s, 1 H, HCO),10.45 (s, 1 H, OH), 14.14 (d, J = 12.8 Hz, 1 H, NH) ppm 13. C NMR (100 MHz, [D 6 ]-DMSO): δ = 22.27, 54.36, 108.94, 116.08, 116.31, 118.59, 120.30, 121.71, 125.43, 126.08, 127.85, 127.92, 146.13, 147.81, 151.66, 155.41, 183.50, 188.65 ppm.…”

Bonding in β-diketiminate boron and its analogues

“…Introduction b-Diketiminato ligand (a) and its derivatives are widely used in organometallic chemistry [1][2][3][4][5][6][7][8]. b-Diketiminato ligand is usually considered as an anion with negative charge delocalized along the NCCCN sequence of atoms (Scheme 1).…”