Molecular engineering of coordination pockets in chloro-tris-phenoxo complexes of titanium(IV)

Nielson, Alastair J.; Shen, Chaohong; Waters, Joyce M.

doi:10.1016/j.poly.2005.12.027

Cited by 25 publications

(26 citation statements)

References 49 publications

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“…[4,19] The reaction of 1 with [K(H 2 -9-BBN)] [20] in hexane is much less complicated. Yields of up to 70 % of compound 11 (δ B = 11.1 ppm) were obtained; see Equation (9). In addition, an 11 B NMR signal at δ = 29.3 ppm was observed resulting from dimeric 9-borabicyclononane 12; 17 % intensity, see also Equation (10).…”

Section: Resultsmentioning

confidence: 92%

“…Steric shielding of the titanium centre in tris(phenolato)-titanium(IV) compounds can be achieved by introducing bulky organyl groups such as methyl, [7] tert-butyl, [8][9][10] isopropyl [11,12] or phenyl groups [7,13,14] into the 2,6-positions of the phenolato ligand. In this study we chose tris(2,6-diisopropylphenolato)titanium(IV) chloride [5] (1), as the starting material, which is readily available, as shown in Equation (1).…”

Section: Resultsmentioning

confidence: 99%

“…Compound 1 can be used for the preparation of methyltris(2,6-diisopropylphenolato)titanium(IV) (2); see Equation (2), which is a precursor of the methylhydridoborate 4, as shown in Equation (4), whereas the reaction of 1 with LiBH 2 R 2 should yield (2,6-iPr 2 C 6 H 3 O) 3 Ti(H 2 BR 2 ) (3). So far, only the structures of five alkyltris(organyloxo)titanium compounds are known, [6,8,9] amongst them methyltris(2,6-diphenylphenolato)titanium(IV) [8] and MeTi[N-(SiMe 3 ) 2 ] 3 . [15] The methyl derivative 2 is susceptible to hydrolysis and photolytic decomposition.…”

Section: Resultsmentioning

confidence: 99%

“…In general, compounds of the type (RO) 4 Ti are monomeric, for example, (2,6-iPrC 6 H 3 O) 4 Ti, [18] (2-tBu-C 6 H 4 O)Ti, [9] (2,3,5,6-Me 4 C 6 HO) 4 Ti [9] and[2,6-Me 2 C 6 H 3 O] 4 -Ti. [29,30] This also holds for several other triorganylphenolatotitanium(IV) compounds, for example, (2,4-tBu 2 C 6 H 3 O) 3 -TiCl, [10] (3,5-tBu 2 C 6 H 3 O) 3 TiI, [31] tris(2,4-tBu 2 C 6 H 4 O) 3 TiCl, [10] (2-PhC 6 H 4 CO) 3 TiCl · OEt 2 [10] and (2,6-Ph 2 C 6 H 3 O) 3 -TiCl.…”

Section: Discussionmentioning

confidence: 99%

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Tris(2,6‐diisopropylphenolato)titanium(IV) Dihydridodiorganylborates: Synthesis and Structures

Knizek

Nöth

2011

Eur J Inorg Chem

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The reactions of tris(2,6‐diisopropylphenolato)titanium(IV) chloride with alkali‐metal dihydridodiorganylborates M(H2BR2) (M = Li, K; R = Me, C6H11, CMe3; BR2 = BC5H10, BC8H14) led to the corresponding titanium dihydridodiorganylborates. However, in almost all cases byproducts such as (2,6‐diisopropylphenolato)diorganylboranes, triorganylboranes, diorganylboranes, diborane and tetrakis(2,6‐diisopropylphenolato)titanium(IV) were also generated. (2,6‐iPr2C6H3O)3Ti(H2BR2) compounds also resulted from the interaction of methyltris(2,6‐diisopropylphenolato)titanium, for example, with catecholborane. In addition to the formation of tris(2,6‐diisopropylphenolato)catecholboratotitanium(IV), B‐methylcatecholborane was also formed The reaction of potassium dihydro‐9‐cyclooctylborate with 2,6‐bis(2,2‐di‐tert‐butyl‐2‐hydroxyethyl)pyridinetitanium dichloride (LTiCl2) led to the complex LTi(H2BC8H14)2. This compound showed no agostic C–H···Ti interaction in contrast to (2,6‐iPr2C6H3O)3TiH2BC8H14 and the corresponding titanium dihydridobis(cyclohexyl)borate.

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Section: Resultsmentioning

confidence: 92%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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Tris(2,6‐diisopropylphenolato)titanium(IV) Dihydridodiorganylborates: Synthesis and Structures

Knizek

Nöth

2011

Eur J Inorg Chem

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“…For bis-phenolato complexes of titanium containing 2-(1,1-dimethylethyl) and 6-methyl subsituents, see: Nielson et al (2005); Santora et al (1999). For some crystal structures of titanium complexes containing terminal and bridging phenolato ligands, see: Gowda et al (2009); Nielson et al (2006); Svetich & Voge (1972).…”

Section: Related Literaturementioning

confidence: 99%

Di-μ-methanolato-bis[(2-tert-butyl-6-methylphenolato-κO)methyltitanium(IV)]

Nielson¹,

Shen²,

Waters³

2013

Acta Cryst E

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The molecule of the title compound, [Ti2(CH3)2(CH3O)2(C11H15O)4] or {[Ti(Me)(μ-OCH3)(OC6H3CMe3-2-Me-6)]2}, has a centrosymmetric, dimeric structure with a distorted square pyramidal array about each titanium atom. The methoxide ligands form an asymmetric bridge between the two TiIV atoms [Ti—O bond lengths of 1.9794 (12) and 2.0603 (12) Å] with the two phenolato ligands occupying the remaining basal sites [Ti—O 1.8218 (11) and 1.8135 (11) Å]. The Ti—O—C phenolato bond angles are similar at 161.24 (10) and 160.66 (11)°. The methyl ligand attached to the metal atom has a Ti—C bond length of 2.0878 (17) Å.

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Coordination Chemistry and Applications of Nitrilotris(N‐Methylenephenoxy)–Metal Complexes

Míriam

Zonta

Licini

2014

Patai's Chemistry of Functional Groups

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Nitrilotris( N ‐methylenephenols), commonly called triphenolamines (TPA), are highly modular, tetradentate molecules that effectively coordinate to transition metals and main group elements with podand topology. They form chiral complexes with intrinsically well‐defined geometries (pentacoordinate trigonal bipyramidal, hexacoordinate octahedral, and, more rarely, trigonal monopyramidal geometries) controlled by the ligand. Nitrilotris( N ‐methylenephenoxy)–metal complexes have been found to be effective and robust catalysts in a series of important processes like polymerizations (titanium(IV), zirconium(VI), hafnium(VI), germanium(VI), and vanadium(V) complexes), oxygen transfer reactions (titanium(VI), vanadium(V), molybdenum(VI), and nickel(II) complexes), carbon–carbon bond formation (aluminium(III), and titanium(VI) complexes), carbon dioxide fixation (iron(III) complexes), and metathesis (Mo(VI) complexes).

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Molecular engineering of coordination pockets in chloro-tris-phenoxo complexes of titanium(IV)

Cited by 25 publications

References 49 publications

Tris(2,6‐diisopropylphenolato)titanium(IV) Dihydridodiorganylborates: Synthesis and Structures

Tris(2,6‐diisopropylphenolato)titanium(IV) Dihydridodiorganylborates: Synthesis and Structures

Di-μ-methanolato-bis[(2-tert-butyl-6-methylphenolato-κO)methyltitanium(IV)]

Coordination Chemistry and Applications of Nitrilotris(N‐Methylenephenoxy)–Metal Complexes

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