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.

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 …

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.

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 …

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.

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…

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?

Carbonyl Transition Metal Complexes of a Silaborate Ligand

Reaction between three equivalents of the silaborate [NEt4][MeSiB10H12] (2) and one equivalent of [Ru3(CO)12] resulted in almost quantitative formation of the mononuclear transition metal complex [NEt4][Ru(CO)3(η5-MeSiB10H10)] (5), which was characterized by X-ray structure analysis. The trinuclear ruthenium complex [NEt4][Ru3(CO)8(η5-MeSiB10H10)] (7) was synthesized in high yield from the reaction of one equivalent of 2 and [Ru3(CO)12]. The cluster 7 reacts with two equivalents of PMe2Ph with substitution of two carbonyl groups to give the substitution product [NEt4][Ru3(CO)6(PMe2Ph)2(η5-MeSiB10H10)] (8).

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…

Hydrogen-Bonded Analogues of Cavitands

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…

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…

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…

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.

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].

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 …

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…

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 …

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…

Wasserstoffbrücken-gebundene Analoga von Cavitanden

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...

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.

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…

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…