Electrophilic Metal Precursors and a β-Diimine Ligand for Nickel(II)- and Palladium(II)-Catalyzed Ethylene Polymerization

Feldman, Jerald; McLain, Stephan J.; Parthasarathy, Anju; Marshall, William J.; Calabrese, Joseph C.; Arthur, Samuel D.

doi:10.1021/om960968x

Cited by 357 publications

(346 citation statements)

References 20 publications

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“…[1] The second route (B) is especially useful for very bulky diWe report herein on the preparation of Ti III (d 1 ) and V III imines, [6] where the route A condensation is very sluggish. (d 2 ) complexes containing a β-diiminato ancillary ligand.…”

Section: Chromiummentioning

confidence: 99%

See 1 more Smart Citation

β-Diiminato Complexes of VIII and TiIII – Formation and Structure of Stable Paramagnetic Dialkylmetal Compounds

Budzelaar¹,

Oort

Orpen

1998

Eur. J. Inorg. Chem.

236

250

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Section: Chromiummentioning

confidence: 99%

“…Lappert has reported a more exotic synthesis ine complexes they showed a much lower activity in Brookof silyl-substituted diiminates from bis(trimethylsilyl)methhart-type olefin polymerization. [2] Collins has recently reyllithium and nitriles. [7] ported the synthesis of several Zr IV complexes of β-diimines.…”

Section: Chromiummentioning

confidence: 99%

β-Diiminato Complexes of VIII and TiIII – Formation and Structure of Stable Paramagnetic Dialkylmetal Compounds

Budzelaar¹,

Oort

Orpen

1998

Eur. J. Inorg. Chem.

236

250

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“…Running the reaction in methylene chloride in the presence of only small amounts of methanol or water, high molecular weight propylene-CO copolymers can be obtained [120]. The combination of [Pd(NCCH 3 ) 4 ](BF 4 ) 2 with a sterically hindered a-diimine ligand results in an ethylene polymerization catalyst, yielding highly branched amorphous ethylene homopolymers [121]. In this case, addition of small amounts of alcohol to the dry chloroform solvent used had no effect on polymer yield.…”

Section: Catalyst Systems Containing Alkyl Aluminum Cocatalystsmentioning

confidence: 99%

“…The system Pd(OAc) 2 /bidentate ligand/ strong acid has also been applied in the absence of CO for the dimerization of olefins, using bidentate ligands (dppp, phen, bipy) in alcohol solvents [129]. By comparison, the system Pd(OAc) 2 /HBF 4 ·Et 2 O/a-diimine has been reported to be active for ethylene polymerization in chloroform solution, in the absence of protic solvents [121].…”

Section: Catalyst Systems Containing Alkyl Aluminum Cocatalystsmentioning

confidence: 99%

Cationic nickel and palladium complexes with bidentate ligands for the CC linkage of olefins

Mecking

2000

Coordination Chemistry Reviews

328

106

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“…The figures generally present digital derivatives in addition to or instead of the original, passage spectrum so that the appearance is consistent with typical EPR spectra, such as those reported elsewhere for such Ni I species. Ni II (OEP) and Ni II (OEiBC) samples in 2-Methf solution were g-irradiated at 77 K. The irradiation was done by Dr. Roman Davydov, Northwestern University, using a Gammacell 200 60 Co irradiator at the University of Chicago Pritzker School of Medicine, using procedures developed by him. 82,84,[89][90][91] The irradiated samples were maintained at 77 K (or lower) throughout the subsequent EPR spectroscopic measurements.…”

Section: Sources Of Complexes Described In Case Studies and Experimenmentioning

confidence: 99%

Overview of ligand versus metal centered redox reactions in tetraaza macrocyclic complexes of nickel with a focus on electron paramagnetic resonance studies

Telser

2010

J. Braz. Chem. Soc.

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Complexos de cobre(II) (3d 9 , S = 1/2) são estáveis e amplamente investigados por espectroscopia de ressonância paramagnética eletrônica (EPR). Já o isoeletrônico níquel(I) é muito menos comum e muito menos estudado. No entanto, níquel(I) tem interesse biológico, uma vez que o sítio ativo da metil coenzima M redutase (MCR) , S = 1/2) complexes are stable and widely investigated by electron paramagnetic resonance (EPR) spectroscopy. In contrast, isoelectronic nickel(I) is much less common and much less investigated. Nickel(I), however, is of biological interest as the active site of methyl coenzyme M reductase (MCR) contains a tetraaza macrocyclic ligand, F 430 , which coordinates Ni I in its active form, MCR red1 . As result, the redox behavior and spectroscopy of tetraaza macrocyclic complexes of nickel is of importance in biomimetic chemistry. Such efforts are complicated by the difficulty in generating Ni I from their stable, Ni II , precursors. Reduction of Ni II macrocyclic complexes can afford Ni I in certain cases, but in many other cases can lead instead to reduction of the macrocycle to generate an organic radical anion. Previous studies on the formation of tetraaza macrocyclic complexes of Ni I are discussed in terms of the competition between metal-centered and ligandcentered reduction. EPR results are particularly important in making the distinction between these two reduction processes, as formation of Ni I gives characteristic EPR spectra similar to those for Cu II , while ligand-centered reduction gives narrow EPR spectra at g = 2.00, typical of organic radicals. Even if metal-centered reduction occurs, the geometry of the resulting Ni I macrocyclic complex is highly variable and, as a result, the EPR spectral appearance is highly variable. In this case, the comparison is between the extremes of spectra typical for tetragonally distorted complexes (dx2-y2 1 ground state, which includes tetragonally distorted octahedral, square pyramidal and square planar geometries) and those for trigonal bipyramidal complexes (dz2 1 ground state). Previous work on Cu II was related to the situation for Ni I . The different types of EPR spectra for such systems are specifically discussed using previously unpublished examples of several tetraaza macrocyclic complexes of nickel, including F 430 and MCR itself.

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Electrophilic Metal Precursors and a β-Diimine Ligand for Nickel(II)- and Palladium(II)-Catalyzed Ethylene Polymerization

Cited by 357 publications

References 20 publications

β-Diiminato Complexes of VIII and TiIII – Formation and Structure of Stable Paramagnetic Dialkylmetal Compounds

β-Diiminato Complexes of VIII and TiIII – Formation and Structure of Stable Paramagnetic Dialkylmetal Compounds

Cationic nickel and palladium complexes with bidentate ligands for the CC linkage of olefins

Overview of ligand versus metal centered redox reactions in tetraaza macrocyclic complexes of nickel with a focus on electron paramagnetic resonance studies

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