Complexes of titanium and zirconium based on [C5Me4CH2-(2-C5H4N)] ligand

Krut’ko, D. P.; Kirsanov, Roman S.; Белов, С. А.; Borzov, Maxim V.; Churakov, Andrei V.

doi:10.1016/j.jorganchem.2006.11.041

Cited by 7 publications

(8 citation statements)

References 35 publications

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“…31 Un like the complex 19•THF, complex 20 does not form the stable solvate with THF, but its crystallization from pyri dine afforded the complex 20•Py as the solvate contain ing one C 5 H 5 N molecule per complex molecule. The molecular structure of 20•Py determined by X ray dif fraction is similar to that of the dimethylamino substi tuted complex 19•THT.…”

Section: Dimethylamino and 2 Pyridyl Substituted Zr IV And Ti Iv Cyclmentioning

confidence: 99%

“…31 Regardless of the nature of the functional group, this method always affords an in separable mixture of three isomers of the target cyclopenta diene (in the case under consideration, 16a-c) and gem dialkyl derivatives 17a,b useless for further synthe ses. 26, 32 The latter compounds are generally formed as the major products (~90%).…”

Section: Dimethylamino and 2 Pyridyl Substituted Zr IV And Ti Iv Cyclmentioning

confidence: 99%

“…31 Dimethylamino substituted half sandwich complex 19 was synthesized by the reaction of silane 14 with ZrCl 4 (THT) 2 in toluene (THT is tetrahydrothiophene). Three complexes, viz., 19, 19•THF, and 19•THT, were obtained depending on the conditions of isolation and purification (Scheme 7).…”

Section: Dimethylamino and 2 Pyridyl Substituted Zr IV And Ti Iv Cyclmentioning

confidence: 99%

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Zirconium and titanium complexes with side-chain functionalized cyclopentadienyl ligands

Krut’ko

2009

Russ Chem Bull

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The present review summarizes the results of studies of Zr and Ti complexes based on chelating side chain functionalized cyclopentadienyl ligands, which were synthesized by the author of the present review and co workers. The coordination ability of the functional groups is considered. Dynamic processes that occur in half sandwich complexes in solutions were studied by NMR spectroscopy. Emphasis is given to the reduction reactions of side chain functionalized zirconocene dichlorides, as well as to the structures and properties of the reaction products depending on the nature of the heteroatomic substituent.The present review summarizes data on Zr and Ti complexes with chelating cyclopentadienyl ligands con taining a functional (heteroorganic) group C 5 R 4 CH 2 CH 2 X (R = H and X = PMe 2 , PPh 2 , P(O)Ph 2 , or P(S)Ph 2 ; R = Me and X = OMe, SMe, NMe 2 , PMe 2 , or PPh 2 ) or C 5 Me 4 CH 2 (2 Py) in the side chain. The types of sand wich and half sandwich complexes I-IV that were syn thesized and investigated are given below.The fundamental and applied interest in studying these compounds is associated with an important feature of these ligands. Thus, these ligands contain two coordina tion sites of different nature, viz., the cyclopentadienyl ring strongly bound to the metal atom and the functional group capable of being involved in the reversible coordi nation. Due to this feature, the ligands are very attractive for the catalyst design, in particular, in the α olefin poly merization, which has stimulated extensive studies in this field from the late 1980s (see the reviews 1-6 ).The presence or absence of the coordination interac tion between the chelating functional group and the metal atom is one of the key factors responsible for the chemi cal, including catalytic, behavior of complexes with side chain functionalized cyclopentadienyl ligands. The coordination ability of chelating heteroatomic functional groups was studied in sufficient detail (primarily by X ray diffraction) for metal complexes in the crystalline state,

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Section: Dimethylamino and 2 Pyridyl Substituted Zr IV And Ti Iv Cyclmentioning

confidence: 99%

Section: Dimethylamino and 2 Pyridyl Substituted Zr IV And Ti Iv Cyclmentioning

confidence: 99%

Section: Dimethylamino and 2 Pyridyl Substituted Zr IV And Ti Iv Cyclmentioning

confidence: 99%

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Zirconium and titanium complexes with side-chain functionalized cyclopentadienyl ligands

Krut’ko

2009

Russ Chem Bull

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“…For the geometric parameters of similar Zr IV complexes, see: Nifant'ev et al (1998); Paolucci et al (2003); Krut'ko et al (2004Krut'ko et al ( , 2007; Enders et al (1996); Nie et al (2008). For Ti IV analogues of the title compound, see: Ge et al (2010) and references cited therein.…”

Section: Related Literaturementioning

confidence: 99%

“…It has been prepared from bis(N,N-dimethyl- (C 16 Among them, there are two dinuclear structures where two Zr-atoms are linked with two bridging µ-Cl-atoms (Enders et al, 1996 andNie et al, 2008; in both cases Zr-atoms exhibit CN 6), two monomeric complexes with a pentacoordinated Zr centre (Nifant'ev et al, 1998 andKrut'ko et al, 2004), and, finally, three monomeric complexes with a hexacoordinated Zr centre (Paolucci et al, 2003;Krut'ko et al, 2004;Krut'ko et al, 2007). Of interest and despite of the different nature of the "sixth" n-donor ligand opposing the Cp-group [a tetrahydrothiophene molecule (Krut'ko et al, 2004), a pyridine molecule (Krut'ko et al, 2007), or a pendant OH-group (Paolucci et al, 2003)], the structural motif of the latter three complexes is very similar to that of I. As for the nature of the Cp-type ligand, only one case among all the mentioned above corresponds to an indenyl group (Nifant'ev et al, 1998).…”

Section: S1 Commentmentioning

confidence: 99%

Trichlorido(tetrahydrofuran){(1,2,3,3a,7a-η)-1-[2-(1-trimethylsilyl-1H-imidazol-2-yl-κN³)-1-methylpropyl]indenyl}zirconium(IV)

2011

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The title compound, [ZrCl 3 (C 19 H 25 N 2 Si)(C 4 H 8 O)], was prepared from bis(N,N-dimethylamido-N)(2-{2-[(1,2,3,3a,-7a-)-indenyl]-2-methylpropyl}-1H-imidazolido-N 1)zirconium(IV) [(C 16 H 16 N 2)Zr(NMe 2)] by reaction with excess Me 3 SiCl in tetrahydrofuran (THF) at elevated temperature. The crystal studied contained a minor non-merohedral twin contaminant [6.3 (4)%] which was taken into account during the refinement. The coordination polyhedron of the Zr IV atom is a distorted octahedron [assuming that the five-membered ring of the indenyl group (Cp) occupies one coordination site], with the Cp group and a THF O atom at the apical positions and the three Cl and ligating N atoms at the equatorial positions. The Zr, Si and the methylene C atoms deviate noticeably from the imidazole ring plane [by À0.197 (5), À0.207 (5) and 0.119 (6) Å , respectively]. The THF ligand adopts an envelope conformation. Related literature For general practical utility of geometry-constrained complexes, including those derived from group 4 transition metals, see: Erker (2006); Braunschweig & Breitling (2006).

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New 1,3-disubstituted side-chain functionalized indenyl ligands and zirconium complexes derived from them

et al. 2010

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New functionalized indenyl ligands Ind X = 1,3 C 9 H 5 (Pr i )(CH 2 CH 2 X) (X = OMe or NMe 2 ) and 1,3 C 9 H 5 (Pr i )[CMe 2 CH 2 (2´ py)] and the zirconium sandwich complexes (Ind X )Cp*ZrCl 2 (Cp* is pentamethylcyclopentadienyl) were synthesized. The photochemical behavior and the reduction reactions of zirconocene dichlorides were investigated. The properties of these compounds are determined mainly by the high lability of Zr-Ind bonds. The reduc tion of (Ind X )Cp*ZrCl 2 (X = NMe 2 ) selectively affords the complex Cp*[η 5 :η 2 (C,N) C 9 H 5 (Pr i )CH 2 CH 2 N(Me)CH 2 ]ZrH as the intramolecular NCH 2 -H bond activation product. The molecular structures of the complex (Ind X )Cp*ZrCl 2 (X = OMe) and its photochemical decomposition product [Cp*ZrCl 2 (OMe)] 2 were established by X ray diffraction.In recent years, it has been shown 1-4 that, due to the unusual η 9 coordination, indenyl ligands containing bulky substituents (SiMe 2 R or Pr i ) at positions 1 and 3 can stabi lize the Zr II center in zirconium sandwich complexes with out loss of high reactivity. In continuation of our studies on the chemistry of functionalized cyclopentadienyl deriv atives of Group IV metals, we synthesized and character ized the complexes [1,3 C 9 H 5 (Pr i )(CR 2 CH 2 X)]Cp*ZrCl 2 (R = H or Me) containing the heteroatomic functional group (X = OMe, NMe 2 , or 2 py) in one of the substitu ents of the five membered ring of the indenyl ligand. In vestigations of the reduction of zirconocene dichlorides and a comparison of these data with the results of our previous research on their tetramethylcyclopentadienyl analogs 5-8 are of particular interest. Results and Discussion Synthesis of ligands and Zr IV complexesDisubstituted indenes 1,3 C 9 H 6 (Pr i )(CH 2 CH 2 X) (X = OMe (1) or NMe 2 (2)) were synthesized by the reac tion of lithium 3 isopropylindenide with ClCH 2 CH 2 X without the isolation of intermediates (Scheme 1). To syn thesize metal complexes, the resulting oily compounds were transformed into the corresponding lithium indenides (Li 1) and (Li 2).

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Complexes of titanium and zirconium based on [C5Me4CH2-(2-C5H4N)] ligand

Cited by 7 publications

References 35 publications

Zirconium and titanium complexes with side-chain functionalized cyclopentadienyl ligands

Zirconium and titanium complexes with side-chain functionalized cyclopentadienyl ligands

Trichlorido(tetrahydrofuran){(1,2,3,3a,7a-η)-1-[2-(1-trimethylsilyl-1H-imidazol-2-yl-κN³)-1-methylpropyl]indenyl}zirconium(IV)

New 1,3-disubstituted side-chain functionalized indenyl ligands and zirconium complexes derived from them

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Complexes of titanium and zirconium based on [C5Me4CH2-(2-C5H4N)] ligand

Cited by 7 publications

References 35 publications

Zirconium and titanium complexes with side-chain functionalized cyclopentadienyl ligands

Zirconium and titanium complexes with side-chain functionalized cyclopentadienyl ligands

Trichlorido(tetrahydrofuran){(1,2,3,3a,7a-η)-1-[2-(1-trimethylsilyl-1H-imidazol-2-yl-κN3)-1-methylpropyl]indenyl}zirconium(IV)

New 1,3-disubstituted side-chain functionalized indenyl ligands and zirconium complexes derived from them

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Trichlorido(tetrahydrofuran){(1,2,3,3a,7a-η)-1-[2-(1-trimethylsilyl-1H-imidazol-2-yl-κN³)-1-methylpropyl]indenyl}zirconium(IV)