Synthesis, structure and ethylene polymerization behavior of titanium phosphinoamide complexes

Highly efficient ethylene/norbornene copolymerization by o‐Di(phenyl)phosphanylphenolate‐based half‐titanocene complexes

“…Among them, half‐metallocene‐type metal complexes are of particular interest and importance from the industrial point of view. Following the success of half‐sandwich titanium amide (constrained geometry) catalysts (CGC), a great deal of examples of Cp'M(L)X 2 have been reported 2–20. Most of them were supported by bi‐, tri‐, and tetradentate chelating and anionic ligands containing, in various combinations, nitrogen and oxygen hard donors.…”

Synthesis and structures of o-phenylene-bridged Cp/phosphinoamide titanium complexes

“…The Ti-P distance (2.6881(19) Å ) is close to those observed for titanium complexes coordinated with phosphine ligand (%2.63 Å ) [14] indicating a chemical bonding between these two atoms, but it is somewhat longer than those observed for the unbridged analogues, Cp * TiCl 2 (g 2 -Ph 2 PNtBu) (2.4928(9) Å ) and Cp * TiCl 2 (g 2 -Ph 2 PNPh) (2.477(2) Å ). 10 By the coordination, C(10)-N-P (129.9(2)°angle is increased from the ideal 120°while Ti-N-P angle (95.93(15)°is contracted. The Ti-N distance (1.935(3) Å ) is longer than those observed for [2-(g 5 -2,3,5-Me 3 C 5 H)-C 6 H 3 NC 6 H 11 ]TiCl 2 (1.9003(13) Å ) 6a and the standard CGC (1.907(4) Å ) 7 but substantially shorter than those observed for the sulfonamide complex, [C 6 H 4 (g 5 -Me 2 -H 2 C 5 )(NTs-jN,O)]TiCl 2 (2.005(5) Å ) 6b and the unbridged complexes Cp * TiCl 2 (g 2 -Ph 2 PNtBu) (2.004(2) Å ) and Cp * TiCl 2 (g 2 -Ph 2 PNPh) (1.983(5) Å ).…”

“…The dramatic chemical-shift change suggests the coordination of the phosphorous atom to the titanium. The coupling constants between phosphorous and C-6 carbon on the phenylene ( 3 J PC ) are not changed significantly by the chlorination (3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14).…”

“…Coordination chemistry utilizing phosphinoamide ligand ([R 2 P-NR 0 ] À ) has drawn extensive attention recently [8]. Bis(phosphinoamido)titanium and zirconium dichloride [9] and unbridged Cp * /phosphinoamide titanium complexes, Cp * TiCl 2 (g 2 -Ph 2 PNR) (R = tBu, nBu, and Ph) [10] were prepared to be tested as a polymerization catalyst …”

Synthesis, ethylene polymerization and dynamic features of titanium and zirconium complexes bearing chelating malonate-based enaminoketonato ligands

“…Group IV metal complexes with a wide range of heteroatom-donor ligands have been prepared and used as catalyst precursors in ethylene polymerization [7][8][9][10][11][12][13][14][15][16][17][18][19]. Complexes bearing (N,O)-type chelating ligands, like Fujita's FI-catalysts, and enaminoketonato-complexes, have attracted considerable interest [20][21][22][23][24].…”