Synthesis, structure and polymerization behavior of tri- and dichloroaminopyridinato complexes of titanium

Talja, M.; Klinga, Martti; Polamo, Mika; Aitola, Erkki; Leskelä, Markku

doi:10.1016/j.ica.2004.11.014

Cited by 29 publications

(30 citation statements)

References 38 publications

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“…3). Cl1-Ti1-Cl2 angle (97.03°) is wider compared to similar angle in Cp 2 TiCl 2 (94.43°) and indicates a comparatively less-hindered Ti-metal center in the latter [39]. Higher yield of complex 8 (87 %) is attributed to clean elimination of HCl gas unlike the poor yield of complex 9 (5 %) perhaps due to the formation of side products (for example Ap 3 TiCl).…”

Section: -7mentioning

confidence: 82%

“…Appl Petrochem Res (2016) 6:307-340 311 elimination reaction (Scheme 5) [39]. To avoid the salt formation, the ligand solution was added dropwise to the TiCl 4 solution, and in such addition method, first, the pyridine part of the ligand coordinates with the metal followed by the bond formation with amido nitrogen.…”

Section: -7mentioning

confidence: 99%

“…However, removal of second chloride to synthesize a bis-Ap complex with the same procedure was not possible. To synthesize bis-Ap complex (9), the ligand was first deprotonated using NaH, and then, sodium salt of the ligand was reacted with TiCl 4 (Scheme 5) [39]. Whereas complex 10 was synthesized by reacting the TiCl 4 (THF) 2 with two equivalents of MeLi and subsequent reaction with sodium salt of aminopyridine ligand (Scheme 6) [39].…”

Section: -7mentioning

confidence: 99%

“…To synthesize bis-Ap complex (9), the ligand was first deprotonated using NaH, and then, sodium salt of the ligand was reacted with TiCl 4 (Scheme 5) [39]. Whereas complex 10 was synthesized by reacting the TiCl 4 (THF) 2 with two equivalents of MeLi and subsequent reaction with sodium salt of aminopyridine ligand (Scheme 6) [39]. Crystal structure of complex 9 has no symmetry elements, and the overall geometry of the complex is distorted octahedral due to presence of two four-membered chelate rings of the two aminopyridinato ligands (Fig.…”

Section: -7mentioning

confidence: 99%

“…Higher yield of complex 8 (87 %) is attributed to clean elimination of HCl gas unlike the poor yield of complex 9 (5 %) perhaps due to the formation of side products (for example Ap 3 TiCl). A better yield of the 9 could be achieved by adding TiCl 4 in a flask followed by the slow addition of ligand [39]. Poor yield of complex 10 (14 %) is linked to the reduction of Ti(IV) into Ti(III) during the reaction.…”

Section: -7mentioning

confidence: 99%

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Aminopyridine stabilized group-IV metal complexes and their applications

Hafeez

Muhammad

2016

Appl Petrochem Res

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During the last two decades, group-IV metalsbased aminopyridinato complexes have attracted a tremendous research interest because of immense industrial needs for the catalyst which would be of higher activity and selectivity with lower toxicity and lower cost. Chemistry of titanium (Ti) and zirconium (Zr) complexes was more extensively explored as compared to hafnium (Hf) complexes. Direct synthesis, salt metathesis, amine elimination, alkane elimination, silyl chloride elimination, hydrogen chloride elimination and toluene elimination protocols have been used for the synthesis of group-IV metal complexes. Changes in ligand and complex design were made to optimize these catalysts for olefin polymerization. Most of these complexes have shown good catalytic activities when activated with dry methyl aluminoxane. Ligand transfer to aluminum was found in these complexes, particularly with less bulky ligands, and this ligand transfer problem was overcome by tridentate ligands but the activities of these complexes were not competitive to complexes with bidentate aminopyridinato ligands. Majority of these complexes produce high-molecularweight polymers with broader molecular weight distributions, and Hf-complexes produce longer chain polymers than their comparative Ti and Zr aminopyridinato complexes. It could be deduced that group-IV metals inherit the potential for optimal polymerizing catalysts probably, because of their almost vacant d-orbitals, these act as hard acids which on combination with soft bases carry the opportunity to design and develop polymerization catalysts which could overcome the problems associated with existing systems.

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Section: -7mentioning

confidence: 82%

Section: -7mentioning

confidence: 99%

Section: -7mentioning

confidence: 99%

Section: -7mentioning

confidence: 99%

Section: -7mentioning

confidence: 99%

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Aminopyridine stabilized group-IV metal complexes and their applications

Hafeez

Muhammad

2016

Appl Petrochem Res

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Enhancing the Value of Free Metals in the Synthesis of Lanthanoid Formamidinates: Is a Co‐oxidant Needed?

Deacon

Junk

Werner

2015

Chemistry A European J

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Treatment of N,N'-bis(aryl)formamidines (ArFormH), N,N'-bis(2,6-difluorophenyl)formamidine (DFFormH) or N,N'-bis(2,6-diisopropylphenyl)formamidine (DippFormH), with europium metal in CH3 CN is an efficient synthesis of the divalent complexes: [{Eu(DFForm)2 (CH3 CN)2 }2 ] (Eu1) or [Eu(DippForm)2 (CH3 CN)4 ] (Eu2). The synthetic method was extended to ytterbium, but the metal required activation by addition of Hg(0) . With DFFormH in CH3 CN, [{Yb(DFForm)2 (CH3 CN)}2 ] (Yb1) was obtained in good yield, and [Yb(DFForm)2 (thf)3 ] (Yb3) was obtained from a synthesis in CH3 CN/THF. Thus, this synthetic method completely circumvents the use of either salt metathesis, or redox transmetallation/protolysis (RTP) protocols to prepare divalent rare-earth formamidinates. Heating Yb1 in PhMe/C6 D6 resulted in decomposition to trivalent products, including one from a CH3 CN activation process. For a synthetic comparison, divalent ytterbium DFForm and DippForm complexes were synthesised by RTP reactions between Yb(0) , Hg(R)2 (R=Ph, C6 F5 ), and ArFormH in THF, leading to the isolation of either [Yb(DFForm)2 (thf)3 ] (Yb3), or the first five coordinate rare-earth formamidinate complex [Yb(DippForm)2 (thf)] (Yb4 b), and, from adjustment of the stoichiometry, trivalent [Yb(DFForm)3 (thf)] (Yb6). Oxidation of Yb3 with benzophenone (bp), or halogenating agents (TiCl4 (thf)2 , Ph3 CCl, C2 Cl6 ) gave [Yb(DFForm)3 (bp)] or [Yb(DFForm)2 Cl(thf)2 ], respectively. Furthermore, the structural chemistry of divalent ArForm complexes has been substantially broadened. Not only have the highest and lowest coordination numbers for divalent rare-earth ArForm complexes been achieved in Eu2 and Yb4 b, respectively, but also dimeric Eu1 and Yb1 have highly unusual ArForm bridging coordination modes, either perpendicular μ-1κ(N:N'):2κ(N:N') in Eu1, or the twisted μ-1κ(N:N'):2κ(N':F') DFForm coordination in Yb1, both unprecedented in divalent rare-earth ArForm chemistry and in the wider divalent rare-earth amidinate field.

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Acetylenetitanium Complex Stabilized by Aminopyridinato Ligands

Noor

Kempe

2008

Eur J Inorg Chem

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The first acetylenetitanium complex stabilized by aminopyridinato ligands has been prepared by the reaction of Ap 2 TiCl 2 (1) -Ap-H = 2-[(2,6-diisopropylphenyl)amino]pyridine -with equimolar amount of bis(trimethylsilyl)acetylene in the presence of magnesium. The complex was characterized by spectroscopic methods as well as by X-ray single crystal structure analysis. Reduction of 1 with KC 8 under N 2 in the absence of

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Synthesis, structure and polymerization behavior of tri- and dichloroaminopyridinato complexes of titanium

Cited by 29 publications

References 38 publications

Aminopyridine stabilized group-IV metal complexes and their applications

Aminopyridine stabilized group-IV metal complexes and their applications

Enhancing the Value of Free Metals in the Synthesis of Lanthanoid Formamidinates: Is a Co‐oxidant Needed?

Acetylenetitanium Complex Stabilized by Aminopyridinato Ligands

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