Journal ArticleDOI
Postmetallocene Lanthanide–Hydrido Chemistry: A New Family of Complexes [{Ln{(Me3Si)2NC(NiPr)2}2(μ-H)}2] (Ln=Y, Nd, Sm, Gd, Yb) Supported by Guanidinate Ligands—Synthesis, Structure, and Catalytic Activity in Olefin Polymerization
Alexander A. Trifonov,Grigorii G. Skvortsov,Dmitrii M. Lyubov,N. A. Skorodumova,Georgii K. Fukin,Evgenii V. Baranov,Valentina N. Glushakova +6 more
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TLDR
The new family of Lewis base free hydrido complexes of rare-earth metals supported by guanidinate ligands was synthesized and structurally characterized and revealed that these complexes are dimeric in both solid state and in [D6]benzene.Abstract:
The new family of Lewis base free hydrido complexes of rare-earth metals supported by guanidinate ligands [{Ln{(Me3Si)2NC(NiPr)2}2(mu-H)}2] (Ln = Y, Nd, Sm, Gd, Yb) was synthesized and structurally characterized. Single-crystal X-ray and solution NMR studies revealed that these complexes are dimeric in both solid state and in [D6]benzene. The dimeric hydrido complexes can adopt eclipsed (Nd, Sm, Gd) or staggered (Y, Yb, Lu) conformations depending on the metal-atom size. Catalytic activity of these [{Ln{(Me3Si)2NC(NiPr)2}2(mu-H)}2] complexes in the polymerization of ethylene, propylene, and styrene has been investigated. Complexes of Sm and Y have high catalytic activity in ethylene polymerization (1268 and 442 g mmol(-1) atm(-1) h(-1), respectively).read more
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Isoprene polymerization with yttrium amidinate catalysts: switching the regio- and stereoselectivity by addition of AlMe3.
TL;DR: The amidinateligated yttrium complex [(NCN)Y(o-CH2C6H4NMe2)2) is a unique catalyst precursor for the polymerization of isoprene and shows extremely high activity and excellent 3,4-isospecificity in the presence of one equivalent of [Ph3C][B(C6F5)4].
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Guanidines: from classical approaches to efficient catalytic syntheses
TL;DR: This review focuses on the metal-mediated catalytic addition of amines to carbodiimides as an atom-economical alternative to the classical synthesis.
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Polymerization catalysis with transition metal amidinate and related complexes
Scott Collins,Scott Collins +1 more
TL;DR: In this paper, the use of transition metal amidinate, guanidinate and amidopyridine complexes to olefin coordination polymerization is reviewed, and a comparison of these complexes with other related ligands is presented.
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‘Old Chemistries’ for new applications: Perspectives for development of precursors for MOCVD and ALD applications
TL;DR: In this paper, the concept of utilizing "old chemistries" for new CVD and ALD applications was highlighted focussing on some representative functional materials namely group IV and rare earth oxides.
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Interdigitated hydrogen bonds: electrophile activation for covalent capture and fluorescence turn-on detection of cyanide.
TL;DR: A xanthene-based fluorescent probe 1, in which tightly held acylguanidine and aldehyde groups engage in multiple intramolecular hydrogen bonds within the concave side of the molecule, provided compelling experimental evidence for the functional role of HBD-HBA interactions in the "remote" control of chemical reactivity.
References
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Thomas Müller,Matthias Beller +1 more
TL;DR: The catalytic production of organic molecules is one of the most important applications of organometallic chemistry and enantioselective syntheses of molecules bearing an amine functionality use classical stoichiometric reactions with chiral auxiliaries or utilize enantiomerically pure starting material.
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.sigma.-Bond metathesis for carbon-hydrogen bonds of hydrocarbons and Sc-R (R = H, alkyl, aryl) bonds of permethylscandocene derivatives. Evidence for noninvolvement of the .pi. system in electrophilic activation of aromatic and vinylic C-H bonds
Mark E. Thompson,Mark E. Thompson,Steven M. Baxter,A. Ray Bulls,Barbara J. Burger,Michael C. Nolan,Bernard D. Santarsiero,William P. Schaefer,John E. Bercaw +8 more
TL;DR: In this article, a structural analysis of hydride and hydrocarbyl derivatives of permethylscandocene has been carried out, and the possibility of involvement of the π-bond system in electrophilic activation of aromatic and vinylic C-H bonds has been examined.
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Synthesis, Structure, and Reactivity of Organometallic .pi.-Complexes of the Rare Earths in the Oxidation State Ln3+ with Aromatic Ligands
Journal ArticleDOI
Preparation of anhydrous lanthanide halides, especially iodides☆
M.D. Taylor,C.P. Carter +1 more
TL;DR: In this article, a general method is described which can be used to synthesize nearly all the lanthanide halides in high purity and good yield, including tri-halides except the iodides of samarium and europium.