Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 64. Darstellung und Kristallstruktur von Bis[N,N′‐bis(trimethylsilyl)benzamidinato]dimethyltitan

Thiele, K.‐H.; Windisch, Harald; Windisch, Heike; Edelmann, Frank T.; Kilimann, Ulrike; Noltemeyer, Mathias

doi:10.1002/zaac.19966220424

Cited by 15 publications

(5 citation statements)

References 17 publications

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“…This makes the Ti−C(10) bond length of 2.207(4) Å in the region of that found in the Ti(II) complex Ti(1,2-(PMe 2 ) 2 CH 2 CH 2 ) 2 Me 2 (2.219(2) Å), but elongated with respect to the distances found in other methyl−titanium complexes with amino, amido, and amidinate substituents (from 2.110 to 2.1385(17) Å). The C−C bond length of the diene group (1.362(7) Å) is similar to reported values for related dad complexes showing a π interaction between the double C−C bond and the metal center (1.371(7)−1.390(4) Å). 5c,d,, …”

Section: Resultssupporting

confidence: 82%

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

et al. 2000

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We report the synthesis of 1,4-diaza-1,3-butadiene (dad) complexes Ti(η 5 -C 5 R 5 )(η 4 -R′ 2 -dad)-Cl (R ) H, Me; R′ ) i Pr, t Bu) by reaction of Ti(η 5 -C 5 R 5 )Cl 3 (R ) H, Me) with the dilithium salts of diisopropyl-and di-tert-butyl-substituted 1,4-diaza-1,3-butadienes (Li 2 [R′ 2 -dad]). Alkylation of the pentamethylcyclopentadienyl diisopropyl and di-tert-butyl derivatives with methylmagnesium chloride and methyllithium gave complexes Ti(η 5 -C 5

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Section: Resultssupporting

confidence: 82%

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

et al. 2000

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“…The X-ray crystalline structures of complexes 16 88,89 and 17 92 have been also reported in the literature and the corresponding crystallographic data for complexes 14 and 15, documented by us, are shown in Fig. 4 and 5 respectively.…”

Section: Synthesis Of Zr and Ti Bis(benzamidinate) Complexessupporting

confidence: 67%

Design of organometallic group iv heteroallylic complexes and their catalytic properties for polymerizations and olefin centered transformations

Smolensky¹,

Eisen²

2007

Dalton Trans.

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The use of metallocenes in many stoichiometric and catalytic processes has been the impetus for the development of new organometallic complexes, especially those containing early transition metals. The formation of coordinative unsaturated complexes using allylic, benzamidinate and aminopyridine families is presented. The synthesis and structural parameters of the new complexes, their activation and use in the polymerization of alpha-olefins and dienes, in the dehydrogenative coupling of silanes and in the hydroamination reactions comprise the objectives of this review.

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“…The crystalline structures of complexes 11 21b,22d and 12 27 have been reported in the literature. The crystallographic data for complexes 9 and 10 are given in Table 10.…”

Section: Resultsmentioning

confidence: 99%

Group 4 Octahedral Benzamidinate Complexes: Syntheses, Structures, and Catalytic Activities in the Polymerization of Propylene Modulated by Pressure

et al. 2003

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The synthesis and structural X-ray diffraction studies for some benzamidinate ligations and several group 4 benzamidinate complexes are presented. The use of the cis-octahedral C(2)-symmetry compounds was studied to shed light on the conceptual applicability of these complexes as potential catalysts for the stereoregular polymerization of propylene. We demonstrate that the stereoregular polymerization of propylene catalyzed by early-transition metal octahedral benzamidinate complexes, activated with either MAO or B(C(6)F(5))(3) as cocatalysts, can be modulated by pressure (from atactic to isotactic through elastomers). The different effects in the polymerization process such as the nature of solvent or cocatalyst, temperature, pressure, molar ratio catalyst:cocatalyst, and the relationship between the symmetry of the complex and the polymer microstructure have been investigated. When the complex [4-CH(3)-C(6)H(4)C(NTMS)(2)](2)ZrMe(2) (9) was activated with MAO, it was found to be a good catalyst for the polymerization of propylene, at atmospheric pressure, producing an oily polymer resembling an atactic polypropylene. Being activated with B(C(6)F(5))(3), complex 9 produces a highly isotactic (mmmm = 98%) product. Likewise, when the polymerization of propylene was performed with complex 9 and MAO at high pressure (liquid propylene), a highly stereoregular polymer was also obtained. Larger activities and stereoregularities were achieved by performing the reaction in CH(2)Cl(2) as compared to toluene. Contrary to complex 9, at atmospheric pressure the complex [4-CH(3)-C(6)H(4)C(NTMS)(2)](2)TiMe(2) (10) is not active either in CH(2)Cl(2) or in toluene. At high pressure, complex 10 produces elastomeric polypropylene. Activities of the isolobal complexes [C(6)H(4)C(NTMS)(2)](2)ZrMe(2) (11) and [C(6)H(4)C(NTMS)(2)](2)TiMe(2) (12) were found to be larger than those of complexes 9 and 10, respectively. Contrary to the structures of the elastomeric polypropylenes described in the literature, the obtained elastomers are characterized by frequent alternation of the isotactic domains with stereodefects. The stereoregular errors are formed by the intramolecular epimerization of the growing chain at the last inserted unit. The epimerization reaction was corroborated through the isomerization of alkenes.

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Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 64. Darstellung und Kristallstruktur von Bis[N,N′‐bis(trimethylsilyl)benzamidinato]dimethyltitan

Cited by 15 publications

References 17 publications

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

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

Design of organometallic group iv heteroallylic complexes and their catalytic properties for polymerizations and olefin centered transformations

Group 4 Octahedral Benzamidinate Complexes: Syntheses, Structures, and Catalytic Activities in the Polymerization of Propylene Modulated by Pressure

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Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 64. Darstellung und Kristallstruktur von Bis[N,N′‐bis(trimethylsilyl)benzamidinato]dimethyltitan

Cited by 15 publications

References 17 publications

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

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

Design of organometallic group iv heteroallylic complexes and their catalytic properties for polymerizations and olefin centered transformations

Group 4 Octahedral Benzamidinate Complexes: Syntheses, Structures, and Catalytic Activities in the Polymerization of Propylene Modulated by Pressure

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

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