Synthesis and catalytic activity of binuclear titanium imido complexes

Said, Musa A.; Hughes, David L.; Bochmann, Manfred

doi:10.1039/b315711c

Cited by 15 publications

(18 citation statements)

References 13 publications

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“…Recently, a reasonably active dimeric titanium m-imido-bridged catalyst was reported by Bochmann et al [61] When activated with MAO the species [TiCl 2 (THF){m-N-3-(PR 2 , respectively, were observed at room temperature. These catalysts were only active for the first few minutes of a 60 minute run, and subsequent results have indicated that bimolecular deactivation occurs following alkylation.…”

Section: Dedicated Cluster Reviewsmentioning

confidence: 96%

Transition Metal Imido Compounds as Ziegler–Natta Olefin Polymerisation Catalysts

2005

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Dedicated to Professor Richard R. Schrock on the occasion of his 60 th birthday in appreciation of his many contributions to organometallic chemistry.Abstract: Transition metal imido compounds having the general formula [(L) n M(NR)] [where (L) n is a supporting ligand or ligand set, and R typically is alkyl or aryl] have been known for nearly 50 years, and during the last two decades have been the focus of considerable attention. Relatively recently their potential application in the Ziegler-Natta polymerisation of olefins has been realised. In this contribution we review the Ziegler-Natta polymerisation of olefins by transition metal imido compounds. A general introduction to homogeneous Ziegler-Natta olefin polymerisation and key aspects of transition metal imido chemistry is given, followed by a short description of a related imidobased polymerisation process, namely ring-opening olefin metathesis polymerisation catalysed by imidosupported molybdenum and tungsten alkylidenes. A summary of the "design principles" that have been employed in the development of certain imido-based Ziegler-Natta catalysts is presented, followed by a comprehensive survey of the literature in the title area.

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Section: Dedicated Cluster Reviewsmentioning

confidence: 96%

Transition Metal Imido Compounds as Ziegler–Natta Olefin Polymerisation Catalysts

2005

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“…11). 18 (7), Zr1-N1 2.111 (7), Zr1-Cl1 2.512 (2), Zr1-N2 2.569 (7), Zr1-Zr2 3.2352 (12), Zr2-N1 2.060 (7), Zr2-N3 2.123 (7), Zr2-N4 2.447 (7), Cg1-Zr1 2.297 (5) (17), Cg1-Zr1-Cl1 103.22 (12), Cg2-Zr2-Cl2 106.92 (11), Cg1-Zr1-Zr2 131.28(9), Cg2-Zr2-Zr1 134.58 (13), C3-C2-C7-N2 62.21 (13), C12-C11-C16-N4 19.25 (13). The amido function from the potentially N,N 0 -chelating ligand, both chelators from the C,N-chelating ligand as well as (11), N1-Hf1-Cl1 107.14(8), N1a-Hf1-Cl1 105.14(8), Cl1-Hf1-Cg1 108.64(9), N1-Hf1-Cg1 125.23 (8), N1a-Hf1-Cg1 122.00(9), N1-Hf1-Hf1a 43.97 (8), N1a-Hf1-Hf1a 41.68 (8), C16-Hf1-Hf1a 164.22 (9).…”

Section: Solid State Studymentioning

confidence: 99%

“…For example, titanium hydrazido and imido complexes containing a pyrrolyl-based ligand are active in hydroamination of alkynes. 12 Both amido-and imidoethylpyridine and aniline N-bridged titanium complexes with the pendant and potentially chelating N-groups ([N(R)(CH 2 CH 2 py)], py ¼ C 5 H 4 N, R ¼ SiMe 3 , Si t BuMe 2 , Ph) were described by Martins. 8 Continuation of work on this topic (for titanium) with simpler and improved synthetic procedures and a plethora of structure descriptions of titanium imides were reported by Lorber.…”

Section: Introductionmentioning

confidence: 99%

“…Selected interatomic distances [Å] and angles [ ]: Hf1-N2 2.055(4), Hf1-C1 2.276(5), Hf1-Cl1 2.4440(13), Hf1-N1 2.463(4), Cg1-Hf1 2.194(4), N2-Hf1-C1 90.01(17), N2-Hf1-Cl1 91.14(11), C1-Hf1-Cl1 133.62(12), N2-Hf1-N1 141.65(15), C1-Hf1-N1 70.87(15), Cl1-Hf1-N1 80.15(10), Cg1-Hf1-Cl1 115.19(12), Cg1-Hf1-N2 106.15(11), C3-C2-C7-N1 30.31(9), N2-H2/N3 2.960(5). Hydrogen atoms are omitted (except of H2) for clarity.…”

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confidence: 99%

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Mixed amido-cyclopentadienyl group 4 metal complexes

et al. 2015

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2 (M ¼ Ti (3), Zr (4), Hf (5)) and(h 5 -C 5 Me 5 )L NN MCl 2 (M ¼ Ti (7), Zr (8), Hf (9)) were prepared from corresponding (pentamethylcyclopentadienyl)metal trichlorides and the lithium precursors L N Li and L NN Li. Besides the desired products a dimeric hafnium compound [(h 5 -C 5 Me 5 ){m-NC 6 H 4 -2-(CH 2 NMe 2 )}HfCl] 2 (10) was also isolated and structurally characterized. The formation of dimeric complexes of this type was also achieved by reacting a series of (h 5 -C 5 Me 4 R)L CN MCl 2 2 )}ZrCl] 2 (16), respectively. The formation of 10 by this reaction procedure was not detected; instead monomeric complexes (h 5 -C 5 Me 4 R) L NN L CN HfCl (R ¼ H (17), Me (18)) were observed as major products. NMR and IR spectroscopy techniques and elemental analysis were used for characterization of the prepared complexes, whereas the structures in most cases were determined by X-ray crystallography. a Scheme 1 Preparation of compounds 3-5.Scheme 2 Synthesis of compound 7.This journal is

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“…Transition‐metal complexes containing nitrogen‐based ligands that can act as a reactive site, such as amido and imido ligands, continue to generate a great deal of interest on account of their crucial roles in many stoichiometric and catalytic reactions, such as olefin metathesis,, Ziegler–Natta polymerization, hydroamination reactions, and ring‐opening metathesis polymerization In addition, owing to their strong π‐donating capabilities and relative inertness, these groups have been used widely in suitable supporting ligands to stabilize high‐valent early transition‐metal complexes. The study of the organometallic chemistry of cyclopentadienyl (Cp) imido complexes of group 5 metals has been stimulated by the isoelectronic relationship between such complexes and the well‐known group 4 bent metallocenes, which are used extensively as α‐olefin polymerization catalysts …”

Section: Introductionmentioning

confidence: 99%

Suitable Approach to Prepare N‐Substituted Niobium Complexes – Study of the Factors Controlling the Process

et al. 2017

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The reactions of the chlorosilyl-substituted cyclopentadienyl niobium compound [Nb(η 5 -C 5 H 4 SiMe 2 Cl)Cl 4 ] (1) with 1 equiv. of 2-methoxyethylamine, 3-methoxypropylamine, and allylamine in toluene specifically afford the corresponding amine adducts [Nb(η 5 -C 5 H 4 SiMe 2 Cl){NH 2 (CH 2 ) n OMe}Cl 4 ] (n = 2, 2; 3, 3) and [Nb(η 5 -C 5 H 4 SiMe 2 Cl)(NH 2 CH 2 CH=CH 2 )Cl 4 ] (4). In contrast, a similar reaction with 1,2-phenylenediamine proceeds with the aminolysis of a Nb-Cl bond and the formation of the amido-amine compound [Nb(η 5 -C 5 H 4 SiMe 2 Cl)(NHC 6 H 4 -2-κNH 2 )Cl 3 ] (5). When such reactions are performed in the presence of 2 equiv. of an additional base, they progress through [a]

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Synthesis and catalytic activity of binuclear titanium imido complexes

Cited by 15 publications

References 13 publications

Transition Metal Imido Compounds as Ziegler–Natta Olefin Polymerisation Catalysts

Transition Metal Imido Compounds as Ziegler–Natta Olefin Polymerisation Catalysts

Mixed amido-cyclopentadienyl group 4 metal complexes

Suitable Approach to Prepare N‐Substituted Niobium Complexes – Study of the Factors Controlling the Process

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