140669-65-4Relevant articles and documents
Mono- and bi-nuclear molybdenum complexes of 2,6-bis(diphenylphosphino)-N-methylaniline
Oort, A. Bart van,Budzelaar, Peter H.M.,Frijns, John H.G.,Orpen, A. Guy
, p. 33 - 47 (1990)
The new ligand 2,6-bis(diphenylphosphino)-N-methylaniline (LH) has been prepared via repeated o-lithiation of lithium N-methyl-N-phenylcarbamate.Reaction of LH with Mo(CO)6 gives Mo(CO)4 (1) and (with an excess of Mo(CO)6) (μ-P,N:P'-LH)M
Preparation of phosphine-amido hafnium and zirconium complexes for olefin polymerization
Jun, Sung Hae,Park, Ji Hae,Lee, Chun Sun,Park, Seong Yeon,Go, Min Jeong,Lee, Junseong,Lee, Bun Yeoul
, p. 7357 - 7365 (2014/04/03)
Aniline (N-R-C6H5NH) and 1,2,3,4-tetrahydroquinoline (2-R-C9H9NH) derivatives were ortho-lithiated via conversion of the respective -NH groups to -N(COOLi), followed by treatment with tBuLi. The resulting ortho-lithiated compounds were transformed to ortho-Ph2P-substituted derivatives on treatment with Ph 2P(OPh). Further reaction of the resulting compounds with M(CH 2Ph)4 (M = Zr, Hf) afforded a series of Hf and Zr complexes: (2-R-8-Ph2PC9H9N)Hf(CH 2Ph)3 (8, R = H; 9, R = Me; 10, R = iPr; 11, R = nBu), (N-R-2-Ph2PC6H4N)Hf(CH2Ph) 3 (12, R = Me; 13, R = Et; 14, R = iPr), (2-R-8-Ph2PC 9H9N)Zr(CH2Ph)3 (15, R = H; 16, R = Me; 17, R = iPr; 18, R = nBu), and (N-R-2-Ph2PC6H 4N)Zr(CH2Ph)3 (19, R = Me; 20, R = Et)]. X-ray crystallographic studies of 9, 14, 16, and 19 revealed a distorted trigonal-bipyramidal structure with two benzyl moieties in equatorial positions and the remaining benzyl ligand occupying an apical position; in solution, however, three benzyl ligands became scrambled, as evidenced by a single set of benzyl signals in the corresponding 1H NMR spectra. The complexes showed comparable activities (17-48 × 106 g/mol-M·h) to the Ti-based constrained geometry catalyst (CGC) (36 × 106 g/mol-Ti·h) in ethylene/1-octene copolymerization, despite their inferior 1-octene incorporation capabilities (3-8 mol % versus 17 mol %). Compound 15 showed a moderate 1-octene incorporation capability (7.7 mol %), whereas the others showed low 1-octene incorporations (2-4 mol %). Compounds 9 and 16 provided high-molecular-weight polymers with Mw > 200 000 even at high reaction temperatures of 100-130 C.
Catalytic scaffolding ligands: An efficient strategy for directing reactions
Lightburn, Thomas E.,Dombrowski, Michael T.,Tan, Kian L.
supporting information; experimental part, p. 9210 - 9211 (2009/02/03)
The design and application of a scaffolding ligand that promotes branch and diastereoselective hydroformylation of terminal olefins as well as the regio- and diastereoselective hydroformylation of disubstituted olefins is reported. It is shown that the ligand covalently and reversibly bonds to the substrate, allowing for directed hydroformylation. As the substrate ligand interaction is dynamic, hydroformylations are catalytic in ligand and do not require any additional synthetic steps to add or remove the directing group. Using a catalytic quantity of a scaffolding ligand (20-25 mol %), excellent regioselectivity for disubstituted olefins (up to 98:2) and high branch selectivity (up to 88:12) for terminal olefins were obtained. Copyright
