Alkyl Complexes (alkyl + complex)

Distribution by Scientific Domains


Selected Abstracts


Synthesis and Reactivity of Rare Earth Metal Alkyl Complexes Stabilized by Anilido Phosphinimine and Amino Phosphine Ligands

CHEMISTRY - A EUROPEAN JOURNAL, Issue 3 2007
Bo Liu
Abstract Anilido phosphinimino ancillary ligand H2L1 reacted with one equivalent of rare earth metal trialkyl [Ln{CH2Si(CH3)3}3(thf)2] (Ln=Y, Lu) to afford rare earth metal monoalkyl complexes [L1LnCH2Si(CH3)3(THF)] (1,a: Ln=Y; 1,b: Ln=Lu). In this process, deprotonation of H2L1 by one metal alkyl species was followed by intramolecular CH activation of the phenyl group of the phosphine moiety to generate dianionic species L1 with release of two equivalnts of tetramethylsilane. Ligand L1 coordinates to Ln3+ ions in a rare C,N,N tridentate mode. Complex l,a reacted readily with two equivalents of 2,6-diisopropylaniline to give the corresponding bis-amido complex [(HL1)LnY(NHC6H3iPr2 -2,6)2] (2) selectively, that is, the CH activation of the phenyl group is reversible. When 1,a was exposed to moisture, the hydrolyzed dimeric complex [{(HL1)Y(OH)}2](OH)2 (3) was isolated. Treatment of [Ln{CH2Si(CH3)3}3(thf)2] with amino phosphine ligands HL2-R gave stable rare earth metal bis-alkyl complexes [(L2-R)Ln{CH2Si(CH3)3}2(thf)] (4,a: Ln=Y, R=Me; 4,b: Ln=Lu, R=Me; 4,c: Ln=Y, R=iPr; 4,d: Ln=Y, R=iPr) in high yields. No proton abstraction from the ligand was observed. Amination of 4,a and 4,c with 2,6-diisopropylaniline afforded the bis-amido counterparts [(L2-R)Y(NHC6H3iPr2 -2,6)2(thf)] (5,a: R=Me; 5,b: R=iPr). Complexes 1,a,b and 4,a,d initiated the ring-opening polymerization of d,l -lactide with high activity to give atactic polylactides. [source]


Unusual Deactivation in the Asymmetric Hydrogenation of Itaconic Acid

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 5 2009
Thomas Schmidt
Abstract During the asymmetric hydrogenation of itaconic acid with rhodium solvate complexes of the type [Rh(PP)(MeOH)2] BF4 (PP=DIPAMP, Me-DuPHOS) a deactivation with increasing substrate concentration is observed. It is shown that this inhibition phenomenon is due to the in situ formation of an inactive rhodium(III)-alkyl complex. Two crystal structures of single crystals of the responsible complexes (1) and (2) support the deactivation pathway. [source]


Cover Picture: (Adv. Synth.

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 18 2009
Catal.
The cover picture, provided by Maurice S. Brookhart, shows an example of a cationic palladium diimine complex which catalyzes polymerization of ethylene to high molecular weight, highly branched polyethylene. The catalyst resting states are the alkyl ethylene complexes as modeled by the ethyl ethylene complex shown. Migratory insertion of these alkyl ethylene species leads to ,-agostic complexes in which palladium can rapidly migrate along the chain ("chain-walking") through ,-elimination/readdition reactions. Trapping of branched alkyl complexes followed by insertion leads to formation of branches in the polymer chain. Polyethylenes formed exhibit branches-on-branches since chain-walking through tertiary centers is facile. [source]


Cover Picture: (Adv. Synth.

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 17 2009
Catal.
The cover picture, provided by Maurice S. Brookhart, shows an example of a cationic palladium diimine complex which catalyzes polymerization of ethylene to high molecular weight, highly branched polyethylene. The catalyst resting states are the alkyl ethylene complexes as modeled by the ethyl ethylene complex shown. Migratory insertion of these alkyl ethylene species leads to ,-agostic complexes in which palladium can rapidly migrate along the chain ("chain-walking") through ,-elimination/readdition reactions. Trapping of branched alkyl complexes followed by insertion leads to formation of branches in the polymer chain. Polyethylenes formed exhibit branches-on-branches since chain-walking through tertiary centers is facile. [source]


Cover Picture: (Adv. Synth.

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 16 2009
Catal.
The cover picture, provided by Maurice S. Brookhart, shows an example of a cationic palladium diimine complex which catalyzes polymerization of ethylene to high molecular weight, highly branched polyethylene. The catalyst resting states are the alkyl ethylene complexes as modeled by the ethyl ethylene complex shown. Migratory insertion of these alkyl ethylene species leads to ,-agostic complexes in which palladium can rapidly migrate along the chain ("chain-walking") through ,-elimination/readdition reactions. Trapping of branched alkyl complexes followed by insertion leads to formation of branches in the polymer chain. Polyethylenes formed exhibit branches-on-branches since chain-walking through tertiary centers is facile. [source]


Cover Picture: (Adv. Synth.

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 14-15 2009
Catal.
The cover picture, provided by Maurice S. Brookhart, shows an example of a cationic palladium diimine complex which catalyzes polymerization of ethylene to high molecular weight, highly branched polyethylene. The catalyst resting states are the alkyl ethylene complexes as modeled by the ethyl ethylene complex shown. Migratory insertion of these alkyl ethylene species leads to ,-agostic complexes in which palladium can rapidly migrate along the chain ("chain-walking") through ,-elimination/readdition reactions. Trapping of branched alkyl complexes followed by insertion leads to formation of branches in the polymer chain. Polyethylenes formed exhibit branches-on-branches since chain-walking through tertiary centers is facile. [source]


Cover Picture: (Adv. Synth.

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 13 2009
Catal.
The cover picture, provided by Maurice S. Brookhart, shows an example of a cationic palladium diimine complex which catalyzes polymerization of ethylene to high molecular weight, highly branched polyethylene. The catalyst resting states are the alkyl ethylene complexes as modeled by the ethyl ethylene complex shown. Migratory insertion of these alkyl ethylene species leads to ,-agostic complexes in which palladium can rapidly migrate along the chain ("chain-walking") through ,-elimination/readdition reactions. Trapping of branched alkyl complexes followed by insertion leads to formation of branches in the polymer chain. Polyethylenes formed exhibit branches-on-branches since chain-walking through tertiary centers is facile. [source]


Cover Picture: (Adv. Synth.

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2009
Catal.
The cover picture, provided by Maurice S. Brookhart, shows an example of a cationic palladium diimine complex which catalyzes polymerization of ethylene to high molecular weight, highly branched polyethylene. The catalyst resting states are the alkyl ethylene complexes as modeled by the ethyl ethylene complex shown. Migratory insertion of these alkyl ethylene species leads to ,-agostic complexes in which palladium can rapidly migrate along the chain ("chain-walking") through ,-elimination/readdition reactions. Trapping of branched alkyl complexes followed by insertion leads to formation of branches in the polymer chain. Polyethylenes formed exhibit branches-on-branches since chain-walking through tertiary centers is facile. [source]


Cover Picture: (Adv. Synth.

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2009
Catal.
The cover picture, provided by Maurice S. Brookhart, shows an example of a cationic palladium diimine complex which catalyzes polymerization of ethylene to high molecular weight, highly branched polyethylene. The catalyst resting states are the alkyl ethylene complexes as modeled by the ethyl ethylene complex shown. Migratory insertion of these alkyl ethylene species leads to ,-agostic complexes in which palladium can rapidly migrate along the chain ("chain-walking") through ,-elimination/readdition reactions. Trapping of branched alkyl complexes followed by insertion leads to formation of branches in the polymer chain. Polyethylenes formed exhibit branches-on-branches since chain-walking through tertiary centers is facile. [source]


Cover Picture: (Adv. Synth.

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2009
Catal.
The cover picture, provided by Maurice S. Brookhart, shows an example of a cationic palladium diimine complex which catalyzes polymerization of ethylene to high molecular weight, highly branched polyethylene. The catalyst resting states are the alkyl ethylene complexes as modeled by the ethyl ethylene complex shown. Migratory insertion of these alkyl ethylene species leads to ,-agostic complexes in which palladium can rapidly migrate along the chain ("chain-walking") through ,-elimination/readdition reactions. Trapping of branched alkyl complexes followed by insertion leads to formation of branches in the polymer chain. Polyethylenes formed exhibit branches-on-branches since chain-walking through tertiary centers is facile. [source]


Cover Picture: (Adv. Synth.

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 7-8 2009
Catal.
The cover picture, provided by Maurice S. Brookhart, shows an example of a cationic palladium diimine complex which catalyzes polymerization of ethylene to high molecular weight, highly branched polyethylene. The catalyst resting states are the alkyl ethylene complexes as modeled by the ethyl ethylene complex shown. Migratory insertion of these alkyl ethylene species leads to ,-agostic complexes in which palladium can rapidly migrate along the chain ("chain-walking") through ,-elimination/readdition reactions. Trapping of branched alkyl complexes followed by insertion leads to formation of branches in the polymer chain. Polyethylenes formed exhibit branches-on-branches since chain-walking through tertiary centers is facile. [source]


Cover Picture: (Adv. Synth.

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 6 2009
Catal.
The cover picture, provided by Maurice S. Brookhart, shows an example of a cationic palladium diimine complex which catalyzes polymerization of ethylene to high molecular weight, highly branched polyethylene. The catalyst resting states are the alkyl ethylene complexes as modeled by the ethyl ethylene complex shown. Migratory insertion of these alkyl ethylene species leads to ,-agostic complexes in which palladium can rapidly migrate along the chain ("chain-walking") through ,-elimination/readdition reactions. Trapping of branched alkyl complexes followed by insertion leads to formation of branches in the polymer chain. Polyethylenes formed exhibit branches-on-branches since chain-walking through tertiary centers is facile. [source]


Cover Picture: (Adv. Synth.

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 5 2009
Catal.
The cover picture, provided by Maurice S. Brookhart, shows an example of a cationic palladium diimine complex which catalyzes polymerization of ethylene to high molecular weight, highly branched polyethylene. The catalyst resting states are the alkyl ethylene complexes as modeled by the ethyl ethylene complex shown. Migratory insertion of these alkyl ethylene species leads to ,-agostic complexes in which palladium can rapidly migrate along the chain ("chain-walking") through ,-elimination/readdition reactions. Trapping of branched alkyl complexes followed by insertion leads to formation of branches in the polymer chain. Polyethylenes formed exhibit branches-on-branches since chain-walking through tertiary centers is facile. [source]


Cover Picture: (Adv. Synth.

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2009
Catal.
The cover picture, provided by Maurice S. Brookhart, shows an example of a cationic palladium diimine complex which catalyzes polymerization of ethylene to high molecular weight, highly branched polyethylene. The catalyst resting states are the alkyl ethylene complexes as modeled by the ethyl ethylene complex shown. Migratory insertion of these alkyl ethylene species leads to ,-agostic complexes in which palladium can rapidly migrate along the chain ("chain-walking") through ,-elimination/readdition reactions. Trapping of branched alkyl complexes followed by insertion leads to formation of branches in the polymer chain. Polyethylenes formed exhibit branches-on-branches since chain-walking through tertiary centers is facile. [source]


Cover Picture: (Adv. Synth.

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 3 2009
Catal.
The cover picture, provided by Maurice S. Brookhart, shows an example of a cationic palladium diimine complex which catalyzes polymerization of ethylene to high molecular weight, highly branched polyethylene. The catalyst resting states are the alkyl ethylene complexes as modeled by the ethyl ethylene complex shown. Migratory insertion of these alkyl ethylene species leads to ,-agostic complexes in which palladium can rapidly migrate along the chain ("chain-walking") through ,-elimination/readdition reactions. Trapping of branched alkyl complexes followed by insertion leads to formation of branches in the polymer chain. Polyethylenes formed exhibit branches-on-branches since chain-walking through tertiary centers is facile. [source]


Cover Picture: (Adv. Synth.

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2009
Catal.
The cover picture, provided by Maurice S. Brookhart, shows an example of a cationic palladium diimine complex which catalyzes polymerization of ethylene to high molecular weight, highly branched polyethylene. The catalyst resting states are the alkyl ethylene complexes as modeled by the ethyl ethylene complex shown. Migratory insertion of these alkyl ethylene species leads to ,-agostic complexes in which palladium can rapidly migrate along the chain ("chain-walking") through ,-elimination/readdition reactions. Trapping of branched alkyl complexes followed by insertion leads to formation of branches in the polymer chain. Polyethylenes formed exhibit branches-on-branches since chain-walking through tertiary centers is facile. [source]


Heterogenization of metalorganic catalysts of olefin polymerization and evaluation of active site non-uniformity

MACROMOLECULAR SYMPOSIA, Issue 1 2004
Lyudmila Novokshonova
Abstract Heterogenized activators - "support-H2O/AlR3" (where R=Me, iBu, support=montmorillonite, zeolite), synthesized directly on the support, form with metallocenes metal alkyl complexes highly active in olefin polymerization without the use of commercial methylaluminoxane (MAO). It was shown by the method of temperature programmed desorption with the application of mass-spectrometry (TPD-MS) that the aluminumorganic compound in support-H2O/AlR3 is in general similar to the structure of commercial MAO. The heterogenization of Zr-cenes on support-H2O/AlR3 is accompanied by the appearance of the energy non-uniformity of active sites. The activation energy of thermal destruction of active Zr-C bonds in the active sites of prepared catalysts changes in the range from 25 to 32 kcal/mol. [source]


Ethyl[tris(3- tert -butyl-5-methylpyrazol-1-yl)hydridoborato]zinc(II)

ACTA CRYSTALLOGRAPHICA SECTION C, Issue 8 2010
Mukesh Kumar
The X-ray crystal structure of the title compound, [Zn(C2H5)(C24H40BN6)], or TptBu,MeZnEt [TptBu,Me is tris(3- tert -butyl-5-methylpyrazolyl)hydridoborate], reveals a distorted tetrahedral geometry around the Zn atom. The Zn center is coordinated by three N atoms of the borate ligand and by one C atom of the ethyl group. The present structure and other tetrahedral Tp zinc alkyl complexes are compared with similar Ttz ligands (Ttz is 1,2,4-triazolylborate), but no major differences in the structures are noted, and it can be assumed that variation of the substitution pattern of Tp or Ttz ligands has little or no influence on the geometry of alkylzinc complexes. Refinement of the structure is complicated by a combination of metric pseudosymmetry and twinning. The metrics of the structure could also be represented in a double-volume C -centered orthorhombic unit cell, and the structure is twinned by one of the orthorhombic symmetry operators not present in the actual structure. The twinning lies on the borderline between pseudomerohedral and nonmerohedral. The data were refined as being nonmerohedrally twinned, pseudomerohedrally twinned and untwinned. None of the approaches yielded results that were unambiguously better than any of the others: the best fit between structural model and data was observed using the nonmerohedral approach which also yielded the best structure quality indicators, but the data set is less than 80% complete due to rejected data. The pseudomerohedral and the untwinned structures are complete, but relatively large residual electron densities that are not close to the metal center are found with values up to three times higher than in the nonmerohedral approach. [source]


Synthesis and Structure of Trialkyltantalum Complexes Stabilized by Aminopyridinato Ligands

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2006
Awal Noor
Abstract (4-Methylpyridin-2-yl)(trimethylsilyl)amine (1), (6-methylpyridin-2-yl)(trimethylsilyl)amine (2), and (2,6-diisopropylphenyl)(pyridin-2-yl)amine (3) were deprotonated and used as ligands to synthesize trialkyltantalum complexes. The reaction of 2 equiv. of 1 or 2 with pentabenzyltantalum afforded tribenzyltantalum(V) complexes by toluene elimination. Analogous reaction using 3 failed. Lithiation of 3 followed by the reaction with tribenzyltantalum dichloride gave rise to the corresponding tribenzyl complex. Other alkyltantalum complexes stabilized by this ligand environment can be prepared by treating tantalum pentachloride with 2 equiv. oflithiated 3 to form a bis(aminopyridinato)tantalum trichloride. The reaction of this trichloride with 3 equiv. of alkyllithium compounds like methyllithium affords the corresponding trialkyltantalum complexes. X-ray diffraction studies of four of the synthesized complexes were carried out. They adopt two different coordination environments, either slightly distorted capped octahedrons (sterically less demanding aminopyridinato ligands) or pentagonal bipyramids (bulkier aminopyridinato ligands). The alkyl species were surprisingly stable at elevated temperatures and no formation of mixed alkyl/alkylidene complexes was observed. Alkyl cation formation and the behaviour of a selection of these compounds in olefin polymerization were explored. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]