Developments of rare earth metal catalysts for olefin polymerization

Nakayama, Yuushou; Yasuda, Hajime

doi:10.1016/j.jorganchem.2004.05.056

Cited by 103 publications

(30 citation statements)

References 55 publications

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“…Such results prompted, until now, a great number of research groups to explore the field of ethylene polymerisation with lanthanide-based catalysts. As reviewed recently [9], almost all of them display at least one Ln-hydride or Ln-alkyl bond, and divalent derivatives can be used alternatively for the same purpose. Among these complexes, lanthanidocenes remain by far the most active.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and X-ray structure of a borohydrido metallocene of neodymium and its use as pre-catalyst in Nd/Mg dual-component ethylene and isoprene polymerisations

Visseaux

Chenal

Roussel

et al. 2006

Journal of Organometallic Chemistry

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Cp* 2 Nd(BH 4 )(THF) (1) (Cp* = C 5 Me 5 ) has been readily obtained in one step from Nd(BH 4 ) 3 (THF) 3 and fully characterized by 1 H NMR, IR spectroscopy, and elemental analysis. Its X-Ray structure displays a neutral monomeric complex, bearing one slightly distorted terminal BH 4group. Associated to nBuEtMg, 1 affords a highly active catalyst for ethylene polymerisation, the first one prepared from a borohydrido organolanthanide pre-catalyst. In the same experimental conditions, the catalytic behaviour of 1 is similar to that of previously described Cp* 2 NdCl 2 Li(Et 2 O) 2 (2). The 1/nBuEtMg system is not deactivated even in the presence of large excesses of THF. In contrast to its chloro homologue 2, the addition of 1 equivalent of nBuEtMg to 1 affords a catalyst for a trans-selective polymerisation of isoprene.2

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Section: Introductionmentioning

confidence: 99%

Synthesis and X-ray structure of a borohydrido metallocene of neodymium and its use as pre-catalyst in Nd/Mg dual-component ethylene and isoprene polymerisations

Visseaux

Chenal

Roussel

et al. 2006

Journal of Organometallic Chemistry

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“…Since the last decade, an impressive number of reports have been devoted to polymerisation catalysis with lanthanide-based catalysts, and particularly in the fields concerning olefins [1,2], conjugated dienes and styrene [3]. Recently, we described the syntheses of (very) uncommon examples of early half-lanthanidocenes, Cp Ã0 LnðBH 4 Þ 2 ðTHFÞ n (Cp Ã0 ¼ C 5 Me n 4 Pr; Ln = Nd, n = 2; Ln = Sm, n = 1) and their use as precatalysts for trans-1,4-stereospecific polymerisation of isoprene in combination with dialkylmagnesium reagents [4,5].…”

mentioning

confidence: 99%

Structural diversity in the borohydrido lanthanides series: First isolation and X-ray crystal structure of ionic

Bonnet

Visseaux

Hafid

et al. 2007

Inorganic Chemistry Communications

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Structural diversity in the borohydrido lanthanides series:First isolation and X-ray crystal structure of ionic ½SmðBH 4 Þ 2 ðTHFÞ 5 þ ½Cp Ã0 SmðBH 4 Þ 3 À AbstractThe reaction of SmðBH 4 Þ 3 ðTHFÞ 3 with a half equivalent of KCp Ã0 ðCp Ã0 ¼ C 5 Me n 4 Pr) affords a compound comprising one Cp Ã0 ligand and three THF molecules per two Sm atoms, ½Cp Ã0 Sm 2 ðBH 4 Þ 5 ðTHFÞ 3 , according to analytical data. Crystals of penta-THF adduct 1, showing the same 1 H NMR spectrum except for the quantity of THF, could be isolated from a solution of half-samarocene Cp Ã0 SmðBH 4 Þ 2 ðTHFÞ (2). X-ray structure determination of 1 revealed an ionic compound ½SmðBH 4 Þ 2 ðTHFÞ 5 þ ½Cp Ã0 SmðBH 4 Þ 3 À with two discrete mononuclear Sm polyhedrons. The expected neutral samarocene Cp Ã0 2 SmðBH 4 ÞðTHFÞ(3) could be obtained from the reaction of SmðBH 4 Þ 3 ðTHFÞ 3 with two equivalents of KCp Ã0 . X-ray structure analysis showed that 3 is a monomeric complex bearing a terminal borohydride ligand. All BH À 4 ligands in 1 and 3 exhibit an g 3 -H 3 BH bonding mode.

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“…Past decades have seen an impressive progress in the design and synthesis of new σ-bonded rare-earth metal alkyl complexes owing to their unique reactivity and the ability to promote various thermodynamically unfavorable reactions, including C−H bond activation and alkane functionalization [1][2][3][4]. Along with the high reactivity in stoichiometric reactions, rare-earth hydrocarbyl complexes hold great promise for catalysis of a wide range of transformations involving unsaturated substrates, such as polymerization (alkenes, dienes, and lactides) [5][6][7][8][9][10][11] hydrogenation [12][13], hydrosilylation [14], hydroamination [15][16][17][18], hydrophosphination (alkenes and alkynes) [19][20][21][22], hydroboration (alkenes) [23,24], and alkyne dimerization [25,26].…”

Section: Introductionmentioning

confidence: 99%

N-Containing Ligands as Universal Coordination Environments for Rare-Earth Alkyl and Bis(alkyl) Complexes

Kissel¹,

Trifonov²

2018

INEOS OPEN

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Developments of rare earth metal catalysts for olefin polymerization

Cited by 103 publications

References 55 publications

Synthesis and X-ray structure of a borohydrido metallocene of neodymium and its use as pre-catalyst in Nd/Mg dual-component ethylene and isoprene polymerisations

Synthesis and X-ray structure of a borohydrido metallocene of neodymium and its use as pre-catalyst in Nd/Mg dual-component ethylene and isoprene polymerisations

Structural diversity in the borohydrido lanthanides series: First isolation and X-ray crystal structure of ionic

N-Containing Ligands as Universal Coordination Environments for Rare-Earth Alkyl and Bis(alkyl) Complexes

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