Optically active titanium complexes containing a tridentate linked amido-cyclopentadienyl ligand

Optically active titanium complexes Ti{η5:η1-C5R4SiMe2NC6H10 (OCH2Ph)-2}Cl2 (R = H, Me), containing a cyclopentadienyl ligand linked to the chiral trans-2-benzyloxycyclohexylamido group, were synthesized and characterized in both enantiomerically pure forms. A single crystal X-ray structure analysis of (−)-(R,R)-Ti{η5:η1-C5H4SiMe2NC6H10(OCH2Ph)-2}Cl2 shows a structure in which the benzyloxy group in the amido sidechain is not interacting with the titanium center. Upon activation with n-butyllithium, these complexes hydrogenate acetophenone N-benzylimine with low enantioselectivity. Chirality 12:472–475, 2000. © 2000 Wiley-Liss, Inc.

Polymerization of ε-caprolactone using heterobimetallic lanthanocene complexes

The chiral heterobimetallic complexes Li[Ln(η 5 :η 1 -C 5 R 4 1 SiMe 2 NCH 2 CH 2 R 2 ) 2 ] (ln= Y, Lu; C 5 R 4 1 = C 5 Me 4 , C 5 H 4 , 3-C 5 H 3 tBu; R 2 = OMe, NMe 2 ) have been found to polymerize e-caprolactone to give a polymer of high molecular weight (M n > 20000) and moderate polydispersity (M w /M n < 2). Failure to observe a correlation between monomer/initiator ratio and molecular weight suggest a polymerization mechanism different from a pseudo-anionic mechanism

Synthesis and structural characterization of titanium complexes containing a sulfinyl-bridged bis(phenolato) ligand

Abstract Titanium complexes containing the novel tridentate 2,2′-sulfinylbis(6-tert-butyl-4-methylphenoxo) ligand (sibmp) were synthesized and characterized. Treatment of titanium tetra-iso-propoxide with 2,2′-sulfinylbis(6-tert-4-methylphenol) (sibmpH2) in 1:1 molar ratio afforded red-orange, sparingly soluble di-iso-propoxo derivative [Ti(sibmp)(O-i-Pr)2]2·0.5 Et2O. The single-crystal structure analysis was performed and revealed a dimeric centrosymmetric structure with a planar Ti2O2 core. The titanium center is approximately octahedral with a SO function intramolecularly coordinated at the titanium center. Treatment of sibmpH2 with titanium tetra-iso-propoxide in 2:1 molar ratio gave y…

Linked amido-indenyl complexes of titanium

Abstract Titanium complexes Ti( η 5 : η 1 -C 9 H 6 SiMe 2 NCMe 3 )X 2 (X = Cl, Me, CH 2 SiMe 3 , CH 2 Ph) containing the tert -amino-functionalized indenyl ligand C 9 H 6 SiMe 3 NCMe 3 have been synthesized by the reaction of the dilithium derivative Li 2 [C 9 H 6 SiMe 2 NCMe 3 ] with TiCl 3 (THF) 3 followed by oxidation or by the alkylation of the dichloro derivative. Unexpectedly, the reaction of C 9 H 6 (SiMe 3 )(SiMe 2 Cl) with TiCl 4 does not give Ti( η 5 -C 9 H 6 SiMe 2 Cl)Cl 3 .

Chelated η5-cyclopentadienyl-η-ethyl complexes of molybdenum and tungsten; molecular structure of W(η5-C5H4CH2-η-CH2)(CO)3

Abstract Molybdenum and tungsten complexes M(η5-C5H4CH2-η-CH2)(CO)3 (M=Mo, W) containing the bidentate ethyl-functionalized cyclopentadienyl ligand C5H4CH2CH2 have been synthesized by the reaction of spiro[2.4]hepta-4,6-diene with M(CO)3L3 (M=Mo; L3=1,3,5-C6H3Me3; M=W; L=NCMe). Reaction of the more stable tungsten complex with C6H5ICl2 and HBF4 gave complexes of the type W(η5-C5H4CH2CH2Cl)(CO)3Cl, W(η5-C5H4CH2CH3)(CO)3Cl and W(η5-C5H4CH2CH3)(CO)3(FBF3), respectively. The crystal structure of the tungsten tricarbonyl complex W(η5-C5H4CH2-η-CH2)(CO)3 has been determined by X-ray crystal diffraction on a single crystal and shows a four-legged piano stool structure.

Complexes of titanium and zirconium containing a tridentate linked amido–cyclopentadienyl ligand with a soft donor group: synthesis, structure, and ethylene polymerization catalysis

Abstract Group 4 metal complexes M(η5:η1-C5R4SiMe2NCH2CH2SMe)Cl2 (R=H, M=Ti; R=Me, M=Ti, Zr) containing the thioether-functionalized linked amido–cyclopentadienyl ligand were synthesized and characterized by 1H- and 13C-NMR spectroscopy, mass spectrometry, and elemental analysis. The crystal structures of the complexes Ti(η5:η1-C5H4SiMe2NCH2CH2SMe)Cl2 and Zr(η5:η1:η1-C5Me4SiMe2NCH2CH2SMe)Cl2 were determined by single-crystal X-ray diffraction studies. The titanium complex is a conventional three-legged piano-stool molecule without an intramolecular interaction between the sulfur donor group and the titanium center, whereas the zirconium complex adopts a trigonal bipyramidal structure, with …

Synthesis and Characterization of Yttrium Complexes Containing a Tridentate Linked Amido−Cyclopentadienyl Ligand

The reaction of dilithium salts of the tridentate linked amido−cyclopentadienyl ligands Li2(C5Me4SiMe2NCH2CH2X) (X = OMe, NMe2, CH2OMe) with [Y(o-C6H4CH2NMe2)Cl2(LiCl)(THF)4] and Y(η5-C5H5)Cl2(THF)3 give chloro-bridged ate complexes of the type [Li(THF)][Y(η5:η1-C5Me4SiMe2NCH2CH2X)(R)Cl], where R = o-C6H4CH2NMe2, η5-C5H5.

Synthesis of branched polyethylenes by the tandem catalysis of silica-supported linked cyclopentadienyl-amido titanium catalysts and a homogeneous dibromo nickel catalyst having a pyridylimine ligand

The synthesis of branched polyethylenes by ethylene polymerization with new tandem catalyst systems consisting of methylaluminoxane-preactivated linked cyclopentadienyl-amido titanium catalysts [Ti(η5:η1-C5Me4SiMe2NR)Cl2 (R = Me or tBu)] supported on pyridylethylsilane-modified silica (PySTiNMe and PySTiNtBu) and homogeneous dibromo nickel catalyst having a pyridyl-2,6-diisopropylphenylimine ligand (PyminNiBr2) in the presence of modified methylaluminoxane was investigated. Ethylene polymerization with only PyminNiBr2 yielded a mixture of 1- and 2-olefin oligomers with methyl branches [weight-average molecular weight (Mw) ∼ 460)] with a ratio of about 1:7. By the combination of this nickel …

Alkyl Complexes of Group 4 Metals Containing a Tridentate-Linked Amido−Cyclopentadienyl Ligand:  Synthesis, Structure, and Reactivity Including Ethylene Polymerization Catalysis

A series of group 4 metal complexes M(η5:η1:η1-C5Me4SiMe2NCH2CH2X)R2 (M = Ti; R = Me, CH2Ph; M = Zr, Hf; R = Me, Et, nPr, nBu, CH2Ph, CH2SiMe3, Ph) containing the tridentate-linked amido−tetramethy...

Dimeric n-Alkyl Complexes of Rare-Earth Metals Supported by a Linked Amido−Cyclopentadienyl Ligand:  Evidence for β-Agostic Bonding in Bridging n-Alkyl Ligands and Its Role in Styrene Polymerization

The dimeric rare-earth hydrides [Ln(η^5:η^1-C_5Me_4SiMe_2NCMe_3)(THF)(μ-H)]_2 (Ln = Y, Yb) react with excess α-olefin H_2C ═ CHR (R = Et, ^nPr, ^nBu) in a 1,2-insertion to give the series of THF-free dimeric n-alkyl complexes [Ln(η^5:η^1-C_5Me_4SiMe_2NCMe_3)(μ-CH_2CH_2R)]_2 as isolable crystals. Single-crystal X-ray diffraction studies on the five derivatives [Y(η^5:η^1-C_5Me_4SiMe_2NCMe_2R‘)(μ-CH_2CH_2R)]_2 (R‘ = Me, R = Et, ^nBu; R‘ = Et, R = Et, ^nPr) and [Yb(η^5:η^1-C_5Me_4SiMe_2NCMe_3)(μ-CH_2CH_2^nBu)]_2 revealed that the centrosymmetric dimeric complexes consist of two trans-arranged [Ln(η^5:η^1-C_5Me_4SiMe_2NCMe_2R‘)] fragments connected by two μ-alkyl ligands. Most strikingly, there…

Activation of C−H Bonds in Five-Membered Heterocycles by a Half-Sandwich Yttrium Alkyl Complex

Zirconium, hafnium and yttrium complexes containing two linked amido— tetramethylcyclopentadienyl ligands: Synthesis, reactivity and molecular structure of Hf(η5:η1−C5Me4SiMe2NiPr)2

Abstract Zirconium and hafnium complexes M(η5: η1−C5Me4SiMe2NR′)xCl(4−2x) (M = Zr, Hf; x = 1, 2; R′ = iPr, tBu) containing one or two linked amido-tetramethylcyclopentadienyl ligands C5Me4SiMe2NR′ have been synthesized by the reaction of the dilithium derivative Li2(C5Me4SiMe2NR′) with MCl4(THF)2. The crystal structure of the hafnium complex Hf(η5: η1−C5Me4SiMe2NiPr)2 has been determined by a single-crystal X-ray diffraction study and shows a C2-symmetric helical metallocene, in which the amido ligands are bonded as π-donor ligands with Hf—N bond lengths of 2.115(2) A. The isoelectronic heterobimetallic yttrium complex Li[Y(η5: η1−C5Me4SiMe2NCH2CH2OMe)2] reacts with phenylacetylene to give …

The Kinetic Stability of Cationic Benzyl Titanium Complexes that Contain a Linked Amido-Cyclopentadienyl Ligand: The Influence of the Amido-Substituent on the Ethylene Polymerization Activity of “Constrained Geometry Catalysts”

Cationic benzyl titanium complexes [Ti(η 5 : η 1 -C 5 Me 4 SiMe 2 NR')-(CH 2 Ph)] + were cleanly formed by the reaction of the dibenzyl titanium complexes [Ti(η 5 : η 1 -C 5 Me 4 SiMe 2 NR')(CH 2 Ph) 2 with B(C 6 F 5 ) 3 and [Ph 3 C][B(C 6 F 5 ) 4 ] in bromobenzene. NMR spectroscopic studies suggest that the benzyl titanium cations contain a fluxional η 2 -coordinated benzyl ligand. Kinetic analysis showed that the benzyl titanium cations decompose according to first-order kinetics and that the amido substituents R' (R' = Me, i Pr, t Bu) in the linked amido-cyclopentadienyl ligand influence the lability of these benzyl titanium cations. The order of the kinetic stability of the benzyl titan…

Optically Active Titanium Complexes Containing Linked Amido‐cyclopentadienyl Ligands: Their Use as Asymmetric Hydrogenation Catalysts

Optically active titanium complexes of the formula Ti(η5:η1−C5R4SiMe2NCHMePh)Cl2 (R = H, Me), containing the cyclopentadienyl ligand linked to a chiral 1-phenylethylamido moiety, were synthesized and characterized in both enantiomerically pure forms. A single-crystal X-ray structural analysis of (S)()Ti(η5:η1−C5H4SiMe2NCHMePh)Cl2 shows a conformation in which the phenyl group is turned away from the metal center. NOE measurements suggest that a related structure is retained in solution. Upon activation with n-butyllithium, these complexes show hydrogenation activity toward imines with slight enantioselectivity.

Titanium complexes having chelating diaryloxo ligands bridged by tellurium and their catalytic behavior in the polymerization of ethylene

A series of titanium complexes having tellurium-bridged chelating bis(aryloxo) ligands, [TiX2{2,2‘-Te(4-R-6-R‘-C6H2O)2}]2 (5b, X = Cl, R = Me, R‘ = tBu; 6a, X = OiPr, R = R‘ = H; 6b, X = OiPr, R = Me, R‘ = tBu), were prepared. 5b and 6b were determined by X-ray crystallography to have chloro- and isopropoxo-bridged dimeric structures. The structural data for these complexes indicated that the Ti−Te coordination bonds were stronger than the similar Ti−S coordination bonds in the corresponding sulfur-bridged complexes. The reaction of (C5R5)TiCl3 (R = H, Me) with 2,2‘-Te(4-R-6-R‘-C6H2OLi)2 gave monocyclopentadienyl derivatives, (C5R5)TiCl{2,2‘-Te(4-Me-6-tBu-C6H2O)2} (7, R = H; 8, R = Me). The…

Pyrrolide-imine benzyl complexes of zirconium and hafnium: synthesis, structures, and efficient ethylene polymerization catalysis

Abstract A series of pyrrolyl-imines HL1–6 was prepared by the condensation of pyrrole-2-carboxyaldehyde with different amines. The reaction of 2 equiv of pyrrolyl-imine with tetrabenzyl complexes of hafnium and zirconium M(CH2Ph)4 (M=Hf or Zr) gave dibenzyl complexes (L3–6)2M(CH2Ph)2, which were characterized by NMR spectroscopy and crystal structure analysis. NMR spectra of the complexes with secondary alkyl substituents at the imine nitrogen (isopropyl: 3a, 4-tert-butylcyclohexyl: 4a and 4b) suggest that rapid racemization between Δ and Λ configurations occurs in solution on the NMR time scale. The complexes with pyrrolide-imine ligands with a tertiary alkyl group such as tert-butyl (5a …

Amphiphile Blockcopolymere mit einem flexiblen Block und einem kettensteifen Segment aus“zylindrischen Bürstenpolymeren”: metallocenkatalysierte Synthese und Bildung von Riesenmicellen

Mono(cyclopentadienyl)titanium complexes containing a sulfide-bridged bis(phenolato) ligand. Molecular structure of Ti{2,2′-S(OC6H2-4-Me-6-tBu)2}(η5-C5H5)Cl

A series of titanium complexes containing a sulfur-bridged chelating bis(phenolato) ligand, Ti{2,2′-S(OC 6 H 2 -4-Me-6- t Bu) 2 }(η 5 -C 5 R 5 )Cl (R=H, Me; R 5 =1,3-(SiMe 3 ) 2 H 3 ), were prepared by the reaction of the dilithium derivative Li 2 [2,2′-S(OC 6 H 2 -4-Me-6- t Bu) 2 ] with Ti(η 5 -C 5 R 5 )Cl 3 . Alkylation of the chloro complexes gave complexes of the type Ti{2,2′-S(OC 6 H 2 -4-Me-6- t Bu) 2 }(η 5 -C 5 R 5 )R′ (R′=Me, CH 2 Ph). The crystal structure of the chloro complex Ti{2,2′-S(OC 6 H 2 -4-Me-6- t Bu) 2 }(η 5 -C 5 H 5 )Cl has been determined by X-ray diffraction and shows a monomeric four-legged piano-stool structure with the sulfur and chlorine atoms in trans positions. …

Ni(II) and Pd(II) complexes of camphor-derived diazadiene ligands: steric bulk tuning and ethylene polymerization

Abstract Nickel(II) and palladium(II) centers were coordinated to a series of chiral 1,4-diazadiene ligands. The ligand backbones are camphor derivatives and the imine nitrogens are attached to independently varied 2- and 2,6-substituted aryl groups. Upon activation with methyl-aluminoxane, the dibromo nickel complexes polymerize ethylene and 1-hexene. The polymerization properties are dependent on the steric features of the aryl substituents on the imine nitrogens.

ChemInform Abstract: Mono(cyclopentadienyl) Complexes of the Rare-Earth Metals

I. Introduction 1953II. Overview of Synthesis, Structure, and Properties 1954A. Synthetic Methods 1954B. Ligands and Structures 1955III. Halo Complexes 1956A. General 1956B. Divalent Halo Complexes 1956C. Trivalent Halo Complexes 1957IV. Chalcogenido Complexes 1958A. General 1958B. Divalent Chalcogenido Complexes 1958C. Trivalent Chalcogenido Complexes 1959V. Pnicogenido Complexes 1960A. General 1960B. Divalent Amido and Phosphido Complexes 1960C. Trivalent Pnicogenido Complexes 19611. Bis(amido) Complexes 19612. Mixed Halo and Chalcogenido Complexes 1962VI. Hydrocarbyl and Silyl Complexes 1963A. General 1963B. Divalent Complexes 19631. Metallacarbaboranes 19632. Bimetallic Naphthalene Comp…

Chiral complexes of titanium containing a linked amido-cyclopentadienyl ligand: synthesis, structure, and asymmetric imine hydrogenation catalysis

Abstract A series of mono- and disubstituted derivatives (−)-(S)-Ti(η5:η1-C5Me4SiMe2NCHMePh)(X)Cl (X=CH2SiMe3, BH4) and (−)-(S)-Ti(η5:η1-C5Me4SiMe2NCHMePh)X2 (X=OSO2CF3, OiPr, Me, CH2Ph) was prepared from (−)-(S)-Ti(η5:η1-C5Me4SiMe2NCHMePh)Cl2 without significant racemization at the stereogenic center. The monosubstituted complexes are formed as mixtures of diastereomers. One diastereomeric monoalkyl (STi, SC)-Ti(η5:η1-C5Me4SiMe2NCHMePh)(CH2SiMe3)Cl was characterized by X-ray single crystal structure analysis. When the (−)-(S)-NCHMePh group is attached to planar chiral ring moieties 3-tBuC5H3, C9H6, and C9H5(SiMe3)-3 and coordinated at the titanium center, diastereomeric mixtures are formed…

Rare earth metal complexes that contain linked amido-cyclopentadienyl ligands: ansa-metallocene mimics and “constrained geometry” catalysts

A survey of group 3 metal complexes that contain a linked amido-cyclopentadienyl ligand is given. Originally designed as ansa-metallocene analogues for the development of single-component olefin polymerization catalysts, variations in the metals and ligand substituents have allowed the synthetic access to new rare earth metal complexes including olefin polymerization initiators, divalent complexes and heterobimetallic metallocenes. The linked amido-cyclopentadienyl ligands have made half-sandwich complexes of group 3 metals accessible in a more systematic manner and provided a better understanding of the electronic and steric constraints of chelating ligands for the larger rare earth metal …

Ring-opening polymerization of lactides using heterobimetallic yttrocene complexes

Structurally characterized, chiral heterobimetallic yttrocene derivatives Li[Y(η 5 :η 1 -C 5 R 4 Si-Me 2 NCH 2 CH 2 OMe) 2 ] (R = Me, H) have been shown to be active in the controlled ring-opening polymerization of L-lactide to give poly(L-lactide)s with high molecular weights and moderately narrow molecular weight distributions (M w /M n < 1.50). Both transesterification and racemization appear to be less prominent. 'H NMR spectroscopic tetrad analysis of copolymers prepared using a mixture of L- and D-lactide demonstrates the absence of any preference for one enantiomer during the polymerization.

Ethylene polymerization catalysts based on nickel(II) 1,4-diazadiene complexes: the influence of the 1,4-diazadiene backbone substituents on structure and reactivity

Abstract Thermally sensitive dialkyl nickel complexes {DAD(H,H)}Ni(CH2SiMe3)2 and {DAD(Me,Me)}Ni(CH2SiMe3)2 [DAD(X,X)=2,6-iPr2C6H4–NC(X)–C(X)N–C6H4iPr2-2,6] were synthesized and were characterized by X-ray diffraction studies on single crystals. The substituents X on the backbone of the α-diimine ligand significantly influence the conformation of the 2,6-diisopropylphenyl substituents. This effect is thought to be of crucial importance for the polymerization of ethylene when {DAD(X,X)}NiBr2/MAO is used as catalyst. The influence of the catalyst structure, pressure, and temperature on the polymerization activity, molar mass, glass transition temperature, melting temperature and branching o…

Alkyl Complexes of Rare-Earth Metals That Contain a Furyl-Functionalized Cyclopentadienyl Ligand:  Alkyl Cation Formation and Unexpected Ring-Opening Reaction of the Furyl Group

Rare-earth metal complexes of the type [Ln{η5:η1-C5Me4SiMe2(C4H3O-2)}(CH2SiMe3)2(THF)] (Ln = Y, Lu) were prepared by σ-bond metathesis of [Ln(CH2SiMe3)3(THF)2] with the 2-furyl-functionalized tetramethylcyclopentadiene (C5Me4H)SiMe2(C4H3O-2) and isolated as colorless crystals. Single-crystal X-ray structure analysis of the lutetium complex confirmed the coordination of the furyl group and THF to give a molecule of trigonal bipyramidal geometry with the oxygen donor atoms in the apical positions. The lability of the oxygen donor atoms results in fluxional behavior. Reaction with triphenylborane in THF gave thermally robust mono(alkyl) cations [Ln{η5:η1-C5Me4SiMe2(C4H3O-2)}(CH2SiMe3)(THF)n]+.…

Rare earth metal-based catalysts for the polymerization of nonpolar and polar monomers

Abstract The synthesis of rare earth metal half-sandwich hydrido complexes [Ln (h5:h1-C5Me 4SiMe2NCMe3) (THF) (µ-H) ] 2 (Ln = Y, Lu) through s-bond metathesis of the easily accessible alkyl complexes [Ln (h5:h1-C5Me 4SiMe2NCMe3) (CH2 SiMe3) (THF) ] was developed. The dimeric yttrium hydrido complexes are highly fluxional, and a monomer-dimer equilibrium is present. They were tested as single-site, single-component catalysts for the polymerization of ethylene and styrene, as well as alkyl acrylate and acrylonitrile. The hydrido complexes polymerize ethylene slowly and form isolable mono (insertion) products with styrene. The yttrium n-alkyl complexes [Y (h5:h1-C5Me 4SiMe2NCMe3) (R) (THF) ] […

Homogeneous ethylene-polymerization catalysts based on alkyl cations of the rare-earth metals: are dicationic mono(alkyl) complexes the active species?

Transition Metal Catalyzed Olefin, Cycloolefin, and Styrene Polymerization

The sections in this article are History and Trends Polymerization Processes Supported Catalysts and Morphology Control Polymerization Mechanisms and Stereoselectivity History and Principles of Metallocene Catalysis Regio- and Stereoselective Polymerization of α-Olefins Polymerization of Cyclic Olefins, Cyclopolymerization, and Stereoselective Polymerization of Styrene Late Transition Metal Catalysts Transition Metal Catalyzed Copolymerization Acknowledgements

Non-bridged amido cyclopentadienyl complexes of titanium: synthesis, characterization, and olefin polymerization catalysis

Alkylation of Ti(η 5 -C 5 Me 5 )(NMe 2 )Cl 2 gives thermally stable, crystalline dialkyl complexes Ti(η 5 -C 5 Me 5 )(NMe 2 )R 2 (R=Me, CH 2 Ph, Ph). The molecular structure of the dibenzyl complex reveals an unprecedented conformation of the doubly bonded NMe 2 group which is turned parallel to the η 5 -C 5 Me 5 ligand, according to single-crystal X-ray diffraction studies. Treatment of the dibenzyl complex with B(C 6 F 5 ) 3 in d 5 -bromobenzene solution results in the quantitative formation of a thermally (>10°C) unstable monobenzyl cation as solvent-separated ion pair [Ti(η 5 -C 5 Me 5 )(NMe 2 )CH 2 Ph] + [PhCH 2 B(C 6 F 5 ) 3 ] − which efficiently polymerizes styrene syndiospecifically…

Di‐ and Trivalent Ytterbium Complexes Containing Linked Amino‐ and Amidocyclopentadienyl Ligands

Reactions of the aminocyclopentadienes (C5Me4H)SiMe2NHR (R = Et, allyl, nPr, tBu) with [YbI2(THF)2] in the presence of two equivalents of potassium 1,2-diphenylethenide in THF at room temperature gave the diamagnetic half-sandwich complexes [Yb(η5-C5Me4SiMe2NHR)Ln(μ-I)]2 (L = THF, n = 2, L = DME, n = 1). The tert-butylamido derivative [Yb(η5-C5Me4SiMe2NHtBu)(THF)2(μ-I)]2 was characterized by X-ray structural analysis as a dinuclear complex containing a nonchelating aminocyclopentadienyl ligand. Deprotonation of the aminocyclopentadiene (C5H4tBu)SiMe2NHtBu with two equivalents of potassium 1,2-diphenylethenide in THF, followed by reaction with [YbI2(THF)2] at 60 °C, gave the trivalent ytterb…

Rare Earth Half-Sandwich Catalysts for the Homo- and Copolymerization of Ethylene and Styrene

The synthesis of rare earth metal half-sandwich hydrido complexes [Ln(η5:η1-C5Me4SiMe2NCMe3)(THF)(μ-H)]2(Ln = Y, Lu, Yb, Er, Tb) through σ-bond metathesis of the alkyl complexes [Ln(η5:η1- C5Me4SiMe2NCMe3)(CH2SiMe3)(THF)], easily accessible by the reaction of the amino-cyclopentadiene with [Ln(CH2SiMe3)3(THF)2], was developed. The dimeric lanthanide hydrido complexes are highly fluxional involving THF dissociation and cis-trans isomerization of the linked amidocyclopentadienyl ligand. The presence of a monomer-dimer equilibrium is suggested by cross-over experiments. They were tested as single-site, single-component catalysts for the polymerization of ethylene, α-olefin, and styrene, as wel…

An Efficient Method for Controlled Propylene Oxide Polymerization: The Significance of Bimetallic Activation in Aluminum Lewis Acids

Aluminum complexes of sterically hindered tetradentate Schiff bases: Synthesis, structure, and reactivity toward ɛ-caprolactone

Abstract The sterically hindered Schiff bases tbmSalenH2 [tbmSalen = N,N′-1,2-ethylenebis(3-tert-butyl-5-methylsalicylideneimine)] and tbmSalcenH2 [tbmSalcen = N,N′-trans-1,2-cyclohexanediyl-bis(3-tert-butyl-5-methylsalicylideneimine)] afforded a series of aluminum complexes of the general formulae [Al(tbmSalen)X] and [Al(tbmSalcen)X] (X = Cl, Me, Et). The molecular structure of [Al(tbmSalcen)Cl] was determined by single-crystal X-ray structural analysis which revealed a five-coordinate aluminum center with a distorted square pyramidal geometry. The alkyl complexes were found to oligomerize ɛ-caprolactone.

ortho-Metalation of aromatic ethers by yttrium alkyl complexes that contain a linked amido-cyclopentadienyl ligand

Abstract The reaction of the half-sandwich alkyl complex [Y(η5:η1-C5Me4CH2SiMe2NtBu)(CH2SiMe3)(THF)] (1) with anisole smoothly gives the ortho-metalation product [Y(η5:η1-C5Me4CH2SiMe2NtBu)(2-C6H4OMe)(THF)] (2). 3- and 4-Methylanisole as well as phenetole analogously undergo ortho-metalation, whereas thioanisole, N,N′-dimethylaniline, fluorobenzene, and trifluorobenzene do not react with yttrium complex 1. 2-Methylanisole reacts with 1 under activation of the ring methyl group to give the 2-methoxybenzyl complex [Y(η5:η1-C5Me4CH2SiMe2NtBu)(CH2C6H4OMe-2)(THF)] (6). A single-crystal X-ray structure analysis of the 2-anisyl complex 2 revealed a four-legged piano-stool configuration with the me…

Copolymerization of ethene with styrene using different methylalumoxane activated half-sandwich complexes

Ethene was copolymerized with styrene using five different methylalumoxane (MAO) activated half-sandwich complexes of the general formula Me 2 Si(Cp)(N-R)MCl 2 , varying the substituents on the cyclopentadienyl ring and the substituent on the amide (Cp = tetramethylcyclopentadiene CBT, 1-indenyl IBT, 3-trimethylsilyl-1-indenyl SIBT, or fluorenyl FBZ, R = tert-butyl (complexes CBT,IBT, SIBT, FBZ ) or benzyl CAT), as well as the metal center ( M = Ti, except FBZ: M = Zr). Polymerization behavior was analyzed with respect to catalyst activity and polymerization kinetics, styrene incorporation, copolymer microstructure, and molecular weight. All complexes produced random poly(ethene-co-styrene)…

Chiral Lanthanocene Derivatives Containing Two Linked Amido−Cyclopentadienyl Ligands:  Heterobimetallic Structure and Lactone Polymerization Activity

Reaction of 2 equiv of dilithium amido−cyclopentadienide Li2(C5R4SiMe2NCH2CH2X) (C5R4 = C5Me4, C5H3tBu; X = OMe, NMe2) with anhydrous LnCl3 (Ln = Y, Lu) gave C2-symmetric complexes of the type Li[Ln(η5:η1-C5R4SiMe2NCH2CH2X)2] containing a heterobimetallic core. The molecular structure of Li[Y(η5:η1-C5Me4SiMe2NCH2CH2OMe)2] was determined by single-crystal X-ray structural analysis, which showed it to exhibit both a pseudotetrahedral yttrium as well as a tetrahedral lithium center. In accordance with a formal 20-electron configuration at the rare earth metal center Ln, the amido-nitrogen atoms are shown to be pyramidalized. In the case of Li[Y(η5:η1-C5H3tBuSiMe2NCH2CH2X)2], mixtures of the tw…

Linked Amido—Cyclopentadienyl Complexes of Group 3 and 4 Metals: The First “Post-Metallocenes”

Linked amido—cyclopentadienyl ligands were introduced by Bercaw and Shapiro in the late eighties with the catalysts of the type Sc(η5:η1-C5Me4SiMe2N t Bu)X (X = H, alkyl) [1]. These electronically more unsaturated and sterically more accessible analogs of ansa-scandocene complexes were found to be capable of catalyzing the living oligomerization of the α-olefins propylene, 1-butene, and 1-pentene. In these complexes the steric constraint [2] of Brintzinger-type ansa-metallocenes is alleviated by the replacement of one cyclopentadienyl ligand by an amido ligand NR’ (Scheme 1). In order to explore sterically demanding derivatives of this dianionic ligand (C5R4ZNR’)2-, iron and titanium comple…

Eine effiziente Methode zur kontrollierten Propylenoxid-Polymerisation: die Bedeutung der Aktivierung durch zwei Metallzentren bei Lewis-Säuren

Ancillary Ligand Effect on Single-Site Styrene Polymerization:  Isospecificity of Group 4 Metal Bis(phenolate) Catalysts

Styrene is polymerized isospecifically by group 4 metal complexes that contain a C2-symmetrically coordinated 1,4-dithiabutane-linked bis(phenolato) ligand activated by methylaluminoxane.

Single-Component Polymerization Catalysts for Ethylene and Styrene:  Synthesis, Characterization, and Reactivity of Alkyl and Hydrido Yttrium Complexes Containing a Linked Amido−Cyclopentadienyl Ligand

Yttrium alkyl complexes Y(η5:η1-C5Me4SiMe2NCMe2R)(CH2SiMe3)(THF) (R = Me, Et) and Y(η5:η1-C9H6SiMe2NCMe3)(CH2SiMe3)(THF) can be prepared in high yields by a σ-bond metathesis reaction between Y(CH2SiMe3)3(THF)2 and amino-functionalized cyclopentadienes or indene. The structure of Y(η5:η1-C5Me4SiMe2NCMe2Et)(CH2SiMe3)(THF) was shown by single-crystal X-ray diffraction to be that of a three-legged piano stool. Reaction of Y(CH2SiMe3)3(THF)2 with the tridentate linked amido−cyclopentadienyl ligands (C5Me4H)SiMe2NHR (R = CH2CH2OMe, CH2CH2NMe2, CH2CH2CH2OMe, CMe2CH2OMe), which contain an additional donor site, results in the cleavage of the silicon−cyclopentadienyl bond and the formation of the t…

Remarkably Robust Group 4 Metal Half-Sandwich Complexes Containing Two Higher Alkyl Ligands:  X-ray Structure and Reactivity of the Di-n-butyl Complex [Hf(η5:η1:η1-C5Me4SiMe2NCH2CH2OMe)nBu2]

The reaction of LiR with M(η5:η1:η1-C5Me4SiMe2NCH2CH2OMe)Cl2 (1, M = Zr (a), Hf (b)) gives the isolable, thermally stable complexes M(η5:η1:η1-C5Me4SiMe2NCH2CH2OMe)R2 (R = Et (2), nPr (3), nBu(4)), which contain two alkyl ligands with β-hydrogen atoms.

Hindering the formation of ferrocenes: mono(cyclopentadienyl)halo iron complexes [Fe(C5R5)X] containing a sterically bulky cyclopentadienyl ligand

Abstract The reaction of lithium 1,2,4-tris(trimethylsilyl)cyclopentadienide Li(Si 3 Cp) with ferrous halide FeX 2 (X=Cl, Br, I) in THF at −95 °C gives a thermally extremely sensitive compound that can be regarded as a functional equivalent for the 14-electron fragment [Fe(Si 3 Cp)X]. Experiments to trap this species with TMEDA gives thermally sensitive, colorless, paramagnetic crystals of the composition [LiFe(Si 3 Cp)Cl 2 (TMEDA) 3 ]. Trimethylphosphite gives isolable 18-electron half-sandwich complexes [Fe(Si 3 Cp){P(OMe) 3 } 2 X]. [Fe(Si 3 Cp)X] is also formed by reducing the ferric derivative [Fe(Si 3 Cp)Cl 2 ] with zinc. Analogous reactivity towards ferrous halides is observed for the…

Titanium Complexes of Chelating Bis(phenolato) Ligands with Long Titanium−Sulfur Bonds. A Novel Type of Ancillary Ligand for Olefin Polymerization Catalysts

The sulfide-linked bis(phenol) tbmpH2 (tbmp = 2,2‘-thiobis(6-tert-butyl-4-methylphenolato)) gives a series of titanium complexes of the formula [Ti(tbmp)X2]2 or [Ti(tbmp)(L)X2] (L = two-electron ligand, X = one-electron ligand). The molecular structures of [Ti(tbmp)(OiPr)2]2 and of [Ti(tbmp){C6H4(CH2NMe2)-2}Cl] were determined by single-crystal X-ray structural analyses. An unusually long titanium−sulfur bond of ∼270 pm is observed in both complexes which contain a six-coordinate titanium center. Variable-temperature NMR spectroscopy shows a fluxional coordination of the chelating aryl group in [Ti(tbmp){C6H4(CH2NMe2)-2}Cl].

Syndiospecific polymerization of styrene using methylaluminoxane-activated bis(phenolato)titanium complexes

Styrene was polymerized using a series of methylaluminoxane-activated bis(phenolato)titanium complexes of the type ((OC 6 H 2 -4-Me-6- 1 Bu) 2 Z)TiX 2 (X = Cl, O 1 Pr, η 5 -C 5 Me 5 ) to give syndiotactic polystyrene. Catalyst activity was found to depend on the nature of the bridging group Z, where Z = CH 2 , CH 2 CH 2 , S, S=O. Activity was found to be highest for Z = S.

Titanium and zirconium complexes that contain a tridentate bis(phenolato) ligand of the [OOO]-type

Abstract The oxygen-linked bis(phenol) 2-oxapropanediyl-1,3-bis(2-tert-butyl-4-methylphenol), [OOO]H2, was prepared in good yield by the condensation of 2-tert-butyl-6-hydroxymethyl-4-methylphenol at 155 °C. This bis(phenol) reacted cleanly with titanium tetrachloride to give the orange titanium dichloro complex [OOO]TiCl2 in virtually quantitative yield. The solubility in pentane indicates a monomeric structure for [OOO]TiCl2 in solution. The reaction of titanium tetra(isopropoxide) gave the di(isopropoxy) complex [OOO]Ti(OiPr)2 which also adopts a monomeric structure of C2v-symmetry in solution. The reaction of the dichloro complex [OOO]TiCl2 with benzyl Grignard reagent in diethyl ether …

Micelle Formation from Amphiphilic“Cylindrical Brush”—Coil Block Copolymers Prepared by Metallocene Catalysis

Zirconium and hafnium mono(alkyl) complexes containing a tridentate linked amido-tetramethylcyclopentadienyl ligand. Molecular structure of Hf(η5:η1:η1-C5Me4SiMe2NCH2CH2OCH3)Cl2

Abstract Zirconium and hafnium complexes M( η 5 : η 1 : η 1 -C 5 Me 4 SiMe 2 NCH 2 CH 2 OMe)Cl 2 (M=Zr, Hf) containing the tridentate 2-methoxyethylamido-functionalized tetramethylcyclopentadienyl ligand C 5 Me 4 SiMe 2 NCH 2 CH 2 OMe have been synthesized by the reaction of the dilithium derivative Li 2 [C 5 Me 4 SiMe 2 NCH 2 CH 2 OMe] with MCl 4 (THF) 2 . Selective monoalkylation of the dichloro complexes gave complexes of the type M( η 5 : η 1 : η 1 -C 5 Me 4 SiMe 2 NCH 2 CH 2 OMe)(R)Cl (R=CH 2 Ph, o -C 6 H 4 CH 2 NMe 2 ). The crystal structure of the hafnium dichloro complex Hf( η 5 : η 1 : η 1 -C 5 Me 4 SiMe 2 NCH 2 CH 2 OMe)Cl 2 has been determined by X-ray crystal diffraction and sho…

Neutral and cationic trimethylsilylmethyl complexes of the rare earth metals supported by a crown ether: synthesis and structural characterization

The synthesis of a series of thermally robust, isolable trimethylsilylmethyl complexes of the rare earth metals stabilized by 12-crown-4 [Ln(CH2SiMe3)3(12-crown-4)] (Ln = Sc, Y, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) is reported. The crystallographically characterized yttrium and lutetium complexes [Ln(CH2SiMe3)3(12-crown-4)] exhibit facial coordination of the crown ether at the neutral lanthanide trialkyl unit. The coordination geometry can be derived from a capped octahedron. VT NMR spectroscopic studies revealed a labile coordination of the crown ether in thf solution. Reaction of the diamagnetic derivatives with triethylammonium tetraphenylborate in thf results in the clean formation of th…

Polymerizations of Cyclic Esters Catalyzed by Titanium Complexes Having Chalcogen-Bridged Chelating Diaryloxo Ligands

A series of titanium complexes having tellurium-bridged chelating bis(aryloxo) ligands, [TiX2{2,2‘-Te(4-Me-6-tBu-C6H2O)2}]2 (5:  X = Cl; 6:  X = OiPr), catalyzed the ring-opening polymerization of cyclic esters such as e-caprolactone, δ-valerolactone, and l-lactide. The strong dependence of polymerizations on the solvent was observed in this catalytic system. When the polymerizations of e-caprolactone and l-lactide were carried out in toluene at 100 °C, tellurium-bridged bis(aryloxo)titanium complex 5 was found to give polymers with rather broad molecular weight distribution due to back-biting. When the polymerizations of e-caprolactone and l-lactide was carried out in anisole or in dioxane…

Hydrogenolysis of the dialkyl complexes [Y(η5-C5Me4SiMe2R)(CH2SiMe3)2(THF)] (1a, R = Me; 1b, R = Ph) results in the formation of the tetranuclear dihydrido complexes [{(η5-C5Me4SiMe2R)Y}4(μ-H)4(μ3-H)4(THF)2] (2a, R = Me; 2b, R = Ph), characterized by NMR spectroscopy. 2a was studied by single crystal X-ray diffraction. In the solid state, an unsymmetrical tetrahedral configuration of four [Y(η5-C5Me4SiMe3)] units is observed, two of which contain each one molecule of THF. Each yttrium atom is bonded to two μ2- as well as three μ3-bridging hydrido ligands. Synthese und Charakterisierung eines vierkernigen Hydrid-Clusters von Yttrium [{η5-(C5Me4SiMe3)Y}4(μ-H)4(μ3-H)4(THF)2] Die Hydrogenolyse …

Dimeric Hydrido Complexes of Rare-Earth Metals Containing a Linked Amido−Cyclopentadienyl Ligand:  Synthesis, Characterization, and Monomer−Dimer Equilibrium

Dimeric hydrido complexes of lutetium, ytterbium, and yttrium containing a linked amido−cyclopentadienyl ligand, [Ln(η5:η1-C5Me4SiMe2NCMe2R)(L)(μ-H)]2 (Ln = Lu, Yb, Y; R = Me, Et; L = THF, PMe3), w...

Mono(cyclopentadienyl) Complexes of the Rare-Earth Metals

I. Introduction 1953II. Overview of Synthesis, Structure, and Properties 1954A. Synthetic Methods 1954B. Ligands and Structures 1955III. Halo Complexes 1956A. General 1956B. Divalent Halo Complexes 1956C. Trivalent Halo Complexes 1957IV. Chalcogenido Complexes 1958A. General 1958B. Divalent Chalcogenido Complexes 1958C. Trivalent Chalcogenido Complexes 1959V. Pnicogenido Complexes 1960A. General 1960B. Divalent Amido and Phosphido Complexes 1960C. Trivalent Pnicogenido Complexes 19611. Bis(amido) Complexes 19612. Mixed Halo and Chalcogenido Complexes 1962VI. Hydrocarbyl and Silyl Complexes 1963A. General 1963B. Divalent Complexes 19631. Metallacarbaboranes 19632. Bimetallic Naphthalene Comp…

Alcoholysis of Aluminum Alkyls Supported by Bulky Phenoxide Ligands: Synthesis, Characterization, and ε-Caprolactone Polymerization Activity of Two Dimeric Aluminum Isopropoxides

Reaction of trialkylaluminum Al2R6 (R = Me, Et) with 2,2′-methylenebis(6-tert-butyl-4-methylphenol) (mbmpH2) gives the dimeric mono(alkyl) complex [Al(mbmp)R]2 with bridging oxygen atoms. Reaction of [Al(mbmp)R]2 with one equiv. of 2-propanol results in the formation of the dimeric isopropoxide [Al(mbmp)(μ-OiPr)]2. Single-crystal X-ray analysis shows a C2h-symmetric structure with a planar Al2O2 core. Monomeric methylbis(2,6-di-tert-butyl-4-methylphenolato)aluminum, AlMe(OC6H2-2,6-tBu2-4-Me)2 (MAD), was found to react with one equiv. of 2-propanol to give a dimeric isopropoxide [AlMe(OC6H2-2,6-tBu2-4-Me)(μ-OiPr)]2 in which the bulky phenolate, instead of the methyl group, has been displaced…

Dialkyl titanium complexes that contain a sulfur-linked bis(phenolato) ligand:

Abstract The sulfur-linked bis(phenol) 2,2′-thiobis(2-tert-butyl-4-methylphenol), tbmpH2, reacted cleanly with titanium tetrachloride to give the orange titanium dichloro complex [Ti(tbmp)Cl2]2 in virtually quantitative yield. Reaction of the dichloro complex [Ti(tbmp)Cl2]2 with methyllithium at low temperature gave the unexpectedly thermally robust, yellow dimethyl complex [Ti(tbmp)Me2]. The reaction of the dichloro complex with benzyl Grignard reagent in pentane afforded the highly crystalline dibenzyl complex [Ti(tbmp)(CH2Ph)2] as a 1,4-dioxane adduct. The single crystal X-ray crystallography revealed a centrosymmetric 1,4-dioxane-bridged molecule that contains two fragments containing s…

Yttrium Alkyl and Hydrido Complexes Containing a Tridentate-Linked Amido-Cyclopentadienyl Ligand

A tridentate-linked amido-cyclopentadienyl ligand (C5Me4CH2SiMe2NCH2CH2NMe2)2- (L) was coordinated at yttrium to give the alkyl complex [Y(L)(CH2SiMe3)(THF)] (2), which reacts with H2 to give the T...

Novel polyolefin materials via catalysis and reactive processing

Recent advances in transition metal catalyzed olefin polymerization and melt processing stimulate the production of new polymers derived from old monomers Modern polyolefin processes do not require polymer purification and give excellent control of molecular and supermolecular polyolefin architectures. Progress in catalyst design and preparation of tailor-made homo-and copolymers is highlighted for isotactic, syndiotactic, atactic and stereoblock polypropylene (PP), novel 1-olefin copolymers, and ethylene copolymers with polar monomers, e.g., CO and acrylics Today polyethylene short-and long-chain-branching is controlled either by uniform ethylene copolymerization with 1-olefins using singl…

Efficient ethylene polymerisation catalysis by a cationic benzyl hafnium complex containing pyrrolide-imine ligandsElectronic supplementary information (ESI) available: experimental and spectroscopic details. See http://www.rsc.org/suppdata/dt/b2/b209582c/

A dibenzyl hafnium(IV) complex containing pyrrolide-imine chelate ligands was synthesized and investigated as an ethylene polymerisation catalyst.

Substituted 1,4-Diaza-1,3-butadiene Monocyclopentadienyl Titanium Complexes. Crystal Structure of Ti(η5-C5Me5)(η4-iPrNCHCHNiPr)Me

We report the synthesis of 1,4-diaza-1,3-butadiene (dad) complexes Ti(η5-C5R5)(η4-R‘2-dad)Cl (R = H, Me; R‘ = iPr, tBu) by reaction of Ti(η5-C5R5)Cl3 (R = H, Me) with the dilithium salts of diisopropyl- and di-tert-butyl-substituted 1,4-diaza-1,3-butadienes (Li2[R‘2-dad]). Alkylation of the pentamethylcyclopentadienyl diisopropyl and di-tert-butyl derivatives with methylmagnesium chloride and methyllithium gave complexes Ti(η5-C5Me5)(η4-iPr2-dad)Me and Ti(η5-C5Me5)(η4-tBu2-dad)Me, respectively. Addition of excess water to di-tert-butyl chloro complexes gave the oxo-bridged complexes [{Ti(η5-C5R5)(η4-tBu2-dad)}2(μ-O)] (R = H, Me). The temperature-dependent spectroscopic behavior of Ti(η5-C5H…

Titanium Complexes with a Linked Amido−Cyclopentadienyl Ligand and a Bidentate Organyl Group: Synthesis, Structure, and Ethene Polymerization Activity

Titanium complexes containing a linked isopropyl- or benzylamido(tetramethylcyclopentadienyl) ligand C5Me4SiMe2NR (R = iPr, CH2Ph,) and one bidentate organyl group C6H4(CH2NMe2)-2, CH2C6H4(NMe2)-2, and {η5-C5H3(CH2NMe2)-2}Fe(η5-C5H5) were prepared by salt metathesis of the corresponding dichloro complex Ti(η5:η1-C5Me4SiMe2NR)Cl2 with the lithium organyl. Single crystal X-ray structural analysis of Ti(η5:η1-C5Me4SiMe2NCH2Ph)- {C6H4(CH2NMe2)-2}Cl and of Ti(η5:η1-C5Me4SiMe2NiPr){CH2C6H4(NMe2)-2}Cl revealed the presence of intramolecular coordination with square pyramidal geometry around titanium. In the ferrocenyl derivative Ti(η5:η1-C5Me4SiMe2NCH2Ph)[{η5-C5H3(CH2NMe2)-2}Fe(η5-C5H5)]Cl the NMe…

Linked cyclopentadienyl-amido titanium catalysts supported on pyridylethylsilane-modified silica for heterogeneous ethylene homo- and copolymerization

Abstract Linked cyclopentadienyl-amido titanium dimethyl and dichloro complexes, Ti(η 5 :η 1 -C 5 Me 4 SiMe 2 N t Bu)X 2 (X=Me, Cl), were reacted with trityl tetrakis(pentafluorophenyl)borate (TB), Ph 3 C + [B(C 6 F 5 ) 4 ] − , and methylaluminoxane (MAO), followed by treatment with toluene suspension of pyridylethylsilane-modified silica, to give two new supported-type titanium catalysts, PySTiTB and PySTiMAO. PySTiTB polymerized ethylene in the presence of triisobutylaluminum (TIBA) in hexane at 60 °C and 5 bar with slightly higher activity than the corresponding homogeneous system under the same conditions. PySTiMAO showed relatively high activity even without any use of alkylaluminum co…

Yttrium Hydrido Complexes that Contain a Less “Constrained Geometry” Ligand:  Synthesis, Structure, and Efficient Hydrosilylation Catalysis

σ-Bond metathesis of the new linked amino-cyclopentadiene (C5Me4H)CH2SiMe2NHCMe3 with Y(CH2SiMe3)3(THF)2 gave the alkyl-yttrium complex [Y(η5:η1-C5Me4CH2SiMe2NCMe3)(CH2SiMe3)(THF)] (1) in 66% yield. Compound 1 was characterized by NMR spectroscopy and X-ray crystal structure analysis. By hydrogenolysis, 1 was quantitatively converted into the dimeric hydride [Y(η5:η1-C5Me4CH2SiMe2NCMe3)(THF)(μ-H)]2 (2). X-ray crystal structure analysis revealed a Y2H2 core connected to two [Y(η5:η1-C5Me4CH2SiMe2NCMe3)(THF)] fragments in a skewed manner, with a relatively long yttrium−yttrium distance of 3.7085(8) A. In solution, two diastereomers were observed by 1H NMR spectroscopy at −78 °C. Dimer 2 was s…

The first structurally characterized cationic lanthanide–alkyl complexesElectronic supplementary information (ESI) available: experimental and spectroscopic details. See http://www.rsc.org/suppdata/cc/b2/b201613n/

Reaction of rare earth metal–alkyl complexes [Ln(CH2SiMe3)3(THF)2] (Ln = Y, Lu) with B(C6X5)3 (X = H, F) in the presence of crown ethers gives crystallographically characterized ion pairs [Ln(CH2SiMe3)2(CE)(THF)n]+[B(CH2SiMe3)(C6X5)3]– (CE = [12]-crown-4, n = 1; CE = [15]-crown-5 and [18]-crown-6, n = 0).

Synthesis and characterization of titanium(IV) complexes containing the diphenylphosphino- and diphenylthiophosphoryl-functionalized cyclopentadienyl ligand. Crystal and molecular structure of Ti(η5-C5H4PPh2)Cl3

The trimethylsilyl cyclopentadiene derivative C5H4(SiMe3)PPh2 (1) was treated with TiCl4 to give the air- and moisture-sensitive mono(cyclopentadienyl) compound Ti(η5-C5H4PPh2)Cl3 (4). Reaction of 4 with Mg(CH2C6H5)2(THF)2 gave Ti(η5-C5H4PPh2)(CH2C6H5)3 (5). Reactions of the lithium and thallium derivatives M{C5H4P(S)Ph2} (M=Li (2), Tl (3)) with one equiv. of TiCl4 afforded the mono(cyclopentadienyl) complex Ti{η5-C5H4P(S)Ph2}Cl3 (6), whereas reaction with 0.5 equiv. of TiCl4 gave the bis(cyclopentadienyl) complex Ti{η5-C5H4P(S)Ph2}2Cl2 (8). Compound 6 was also isolated as a minor product from the reaction of Ti{η5-C5H4P(S)Ph2}2Cl2 (8) with one equiv. of TiCl4. The major product was identif…

Group 3 and 4 metal alkyl and hydrido complexes containing a linked amido-cyclopentadienyl ligand: “constrained geometry” polymerization catalysts for nonpolar and polar monomers

Abstract In order to understand the nature of the putative cationic 12-electron species [M(η 5 :η 1 -C 5 R 4 SiMe 2 NR′)R″] + of titanium catalysts supported by a linked amido-cyclopentadienyl ligand, several derivatives with different cyclopentadienyl C 5 R 4 and amido substituents R′ were studied systematically. The use of tridentate variants (C 5 R 4 SiMe 2 NCH 2 CH 2 X) 2− (C 5 R 4 =C 5 Me 4 , C 5 H 4 , C 5 H 3 t Bu ; X=OMe, SMe, NMe 2 ) allowed the NMR spectroscopic observation of the titanium benzyl cations [Ti(η 5 :η 1 -C 5 Me 4 SiMe 2 NCH 2 CH 2 X)(CH 2 Ph)] + . Isoelectronic neutral rare earth metal complexes [Ln(η 5 :η 1 -C 5 R 4 SiMe 2 NR′)R″] can be expected to be active for pol…

Metalation of aromatic heterocycles by yttrium alkyl complexes that contain a linked amido-cyclopentadienyl ligand: synthesis, structure and Lewis base adduct formation

Abstract The reaction of the half-sandwich alkyl complex [Y(η5:η1-C5Me4SiMe2NCMe3)(CH2SiMe3)(THF)] with furan and thiophene gives metalation products [Y(η5:η1-C5Me4SiMe2NCMe3)(μ-2-C4H3X)]2 (X=O, S) which are sparingly soluble in hydrocarbons due to the dimeric structure. Single crystal X-ray structure analysis of the 2-thienyl complex confirms a six-membered core with bridging sulfur atoms and trans-disposed amido-tetramethylcyclopentadienyl ligands. In contrast to THF and pyridine, 1,2-dimethoxyethane (DME) forms isolable, crystalline adducts [Y(η5:η1-C5Me4SiMe2NCMe3)(2-C4H3X)(DME)]. Single crystal X-ray structure analysis of the 2-furyl derivative shows a four-legged piano stool configura…

Tritylpyridinium tetrakis(pentafluorophenyl)borate as an efficient activator for “constrained-geometry” catalysts in ethylene polymerization

Abstract Ethylene polymerization with linked amido-cyclopentadienyl or “constrained-geometry” titanium catalysts, Ti(η 5 :η 1 -C 5 Me 4 SiMe 2 N t Bu)X 2 (X=Me, Bz, Cl), activated by tritylpyridinium tetrakis(entafluorophenyl)borate, [Ph 3 C(NC 5 H 5 )] [B(C 6 F 5 ) 4 ], and silica-supported tritylpyridinium tetrakis(entafluorophenyl)borate (PySTB) was found to proceed with high activity. 1 H NMR spectra in CD 2 Cl 2 suggest that ([Ti(η 5 :η 1 -C 5 Me 4 ,SiMe 2 N t Bu)Me (NC 5 H 5 )] + is formed as the main cationic species. Using the heterogeneous cocatalyst PySTB in hexane, unexpectedly high ethylene polymerization activity was achieved, giving high molecular weight polyethylenes with exc…

Linked Benzylamido-Cyclopentadienyl Ligands: Synthesis and Characterization of Alkyl Titanium Complexes

Titanium complexes of the general type Ti(η5:η1-C5H4Si-Me2NCH2C6H3X2-2,5)Cl2 (XH, F), containing a linked benzylamido-cyclopentadienyl ligand, were prepared by reaction of Ti(η5-C5H4SiMe2Cl)Cl3 with lithium amide Li(NHCH2C6H3X2-2,5). A single-crystal X-ray structural analysis of Ti(η5: η1-C5H4SiME2NCH2C6H3F2-2,5)Cl2 revealed a conformation in the solid state in which the aryl ring is turned away from the metal center. Ti(η5:η1-C5H4SiMe2NCH2C6H5)Cl2 can be alkylated with a variety of reagents to form extremely sensitive complexes of the type Ti(η5-C5H4SiMe,2NCH2C6H5)R2 (RMe, CH2 C6H5, CH2SiME3, CH2CMe2C6H5). Reaction of Li2[C5Me4SiMe2NCH2C6H5] with TiCl3(THF)3 gave Ti(η5: η1-C5Me4SiMe2NCH2C6…