Trinuclear Titanium Research Articles

A novel trinuclear titanium(IV) complex with a C3 axis along Ti1–Ti2–Ti3 containing 3-[(1 H-1,2,4-triazol-1-yl)methyl]-BINOLate ligands: synthesis, structure, and reactivity

A new modified BINOL, ( S)-3-[(1 H-1,2,4-triazol-1-yl)methyl]-1,1′-binaphthol, was prepared. In the presence of titanium tetraisopropoxide, this ligand showed moderate catalytic properties for the asymmetric addition of diethylzinc to aldehydes. By treating rac-3-[(1 H-1,2,4-triazol-1-yl)methyl]-1,1′-binaphthol with excess titanium tetraisopropoxide, a novel trinuclear titanium(IV) complex was obtained. A C 3 axis along Ti1–Ti2–Ti3 is present in the molecule.

Crystal Structure of a Trinuclear Titanium(IV) Complex with (rac)‐3,3′‐Bis(methoxymethyl)‐BINOLate

AbstractReaction of (rac)‐3,3′‐bis(methoxymethyl)‐BINOL [H2(CH3OCH2)2BINO] with excess Ti(OiPr)4 and one equivalent of H2O in CH2Cl2 affords a trinuclear titanium(IV) complex [{(CH3OCH2)2BINO}Ti3(μ3‐O)(OiPr)6(μ2‐OiPr)2]. By dissolving it in dichloromethane and hexane and cooling to 0 °C, plate‐like pale yellow single crystals (monoclinic, P21/n, a = 12.605(3), b = 21.994(5), c = 19.090(4) Å, β = 92.764(8)°, V = 5286.2(19) Å3, T = 293(2) K) were obtained. Each oxygen atom at 2 or 2′ position of the (CH3OCH2)2BINO ligand bonds to only one titanium atom. There is no interaction between the third Ti atom and the two oxygen atoms of 3,3′‐bis(methoxymethyl)‐BINOLate.

Iodine Attack on the Metalloligand [{Ti(η5‐C5Me5)(μ‐NH)}3(μ3‐N)]: Surprising Formation of the [Ti3(η5‐C5Me5)3I2(μ‐NH)3(NH3)]+ Cation

AbstractThe reactivity of the trinuclear imido‐nitrido complex [{Ti(η5‐C5Me5)(μ‐NH)}3(μ3‐N)] (1) and derivatives thereof withiodine has been investigated. Treatment of the indium(I)adduct [IIn{(μ3‐NH)3Ti3(η5‐C5Me5)3(μ3‐N)}] (2) with I2 (1 equiv.) in benzene afforded the indium(III) complex [I3In{(μ3‐NH)3Ti3(η5‐C5Me5)3(μ3‐N)}] (3), but with excess of iodine the precipitation of orange crystals of the ionic complex [Ti3(η5‐C5Me5)3I2(μ‐NH)3(NH3)][InI4] (4) takes place. Analogous treatment of the metalloligand 1 with I2 in toluene gave initially the iodine(I) derivative [I{(μ3‐NH)3Ti3(η5‐C5Me5)3(μ3‐N)}][I3] (5). Surprisingly, toluene solutions of 5 at room temperature produced crystals of the ionic complex [Ti3(η5‐C5Me5)3I2(μ‐NH)3(NH3)][I3]·C7H8 (6·C7H8). The trinuclear titanium cation [Ti3(η5‐C5Me5)3I2(μ‐NH)3(NH3)]+ of complexes 4 and 6 has been structurally characterized by a combination of X‐ray and DFT studies. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Synthesis, structures, and solution behavior of di- and trinuclear titanium(IV)--cyclophosphato complexes.

The reaction of the cyclotetraphosphate ion (P(4)O(12)(4)(-)) with [CpTiCl(3)] (Cp = eta(5)-C(5)Me(5)) gives [(CpTi)(2)(P(4)O(12))(2)](2)(-) where the P(4)O(12) ligands adopt a saddle conformation, while that with [(CpTiCl)(3)(mu-O)(3)] leads to [(CpTi)(3)(mu-O)(3)(P(4)O(12))](-) containing a crown form P(4)O(12) ligand; both products feature their unique cage structures. On the other hand, the reactions of the cyclotriphosphate ion (P(3)O(9)(3)(-)) with [(CpTiCl(2))(2)(mu-O)] and [(CpTiCl)(3)(mu-O)(3)] afford [(CpTi)(2)(mu-O)(P(3)O(9))(2)](2)(-) and [(CpTi)(3)(mu-O)(3)Cl(P(3)O(9))](-), respectively, and in both cases the P(3)O(9) ligands bridge two titanium centers with an eta(2):eta(1) mode.

An open chain trinuclear titanium(IV) isopropoxide species formed with the tridentate ligand cis,cis–cyclohexane–1,3,5-trialkoxide [C6H9O3]3−. Crystal structure of [{Ti(OPri)3}2{μ-Ti(C6H9O3-O1,O5)2}

Reaction of titanium(IV) tetraisopropoxide with cis,cis-cyclohexane-1,3,5-triol [C6H9(OH)3, H3L] affords the novel trinuclear titanium(IV) alkoxide species [{Ti(OPri)3}2{µ-Ti(C6H9O3-O1,O5)2}] {L = [C6H9O3]3–} which possesses a unique open-chain V-shaped arrangement of three titanium atoms, with the central 6-co-ordinate Ti atom bonded to two tridentate L groups, and with each of the two terminal Ti atoms 5-co-ordinate, forming bonds to three non-bridging isopropoxide groups, and to two bridging oxygen atoms, one from each of the two ligands L.

ChemInform Abstract: Synthesis and X‐Ray Structure of a Novel Chiral Trinuclear Titanium‐ Tetraol Complex.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Synthesis and X-ray structure of a novel chiral trinuclear titanium-tetraol complex

This paper describes the synthesis of the chiral tetraol 1, and its conversion with Ti(IV) 1,1,1,3,3,3-hexafluoroisopropoxide to the novel linear trinuclear titanium complex 8 whose structure has been determined by spectroscopic and X-ray crystallographic analysis.

Darstellung, struktur und eigenschaften des dreikernigen titankomplexes (π-C 2H 5) 2TiClOTi(π-C 5H 5)ClOTiCl(π-C 5H 5) 2·CHCl 3

The trinuclear titanium(IV) complex (π-C 5H 5) 2TiClOTi(π-C 5H 5)ClOTiCl(π-C 5H 5) 2 · CHCl 3 is formed by hydrolysis of (π-C 5H 5) 2TiCl 2 at pH > 3.5 and can be isolated in the crystalline state from the reaction of (π-C 5H 5) 2TiCl 2 with Ag 2O and water in chloroform. Its structure is determined by X-ray analysis.