Titanium Center Research Articles

Heterobimetallic Samarium(III) and Titanium(IV) Complexes with Bifunctional Catalytic Properties

Reaction of the bis-ligand-chelated samarium complex [Sm(Hbptd)(H2bptd)] (1; H3bptd =1,9-bis(2-pyrrolyl)-2,5,8-triazanona-1,8-diene), in which a pyrrolyl ring is dangling and metal-free, with Ti(NMe2)4 yielded the heterometallic complex [Sm(Hbptd)(THF)(bptd)Ti(NMe2)2] (2). Treatment of the H3bptd ligand with 1 equiv of Ti(NMe2)4 gave the titanium amido complex [Ti(bptd)(NMe2)] (3). Complexes 2 and 3 were able to catalyze the hydroamination of phenylacetylene with 2,4-dichloroaniline and 4-methoxyaniline, and high regioselectivities were observed for the two amines. Both 1 and 2 were active catalysts for the ring-opening polymerization of ε-caprolactone. 2 showed higher activity for the polymerization reactions, due to a decrease in the coordination number of the samarium atom (from 9 in 1 to 8 in 2) by sharing its ligand with the titanium center.

Effect of water adsorption on the structural and optical properties of silicon and titanium dioxide nanoclusters

The formation of the structure and infrared (IR) spectra of (SiO2)n (n = 1–4) and (TiO2)n (n = 1–3) clusters with an increase in their size n has been simulated using the B3LYP/6-31G* method of the density functional theory. The effect that water adsorption has on the structural and optical properties of silicon and titanium dioxide nanoclusters has been studied by this method as well. The calculated IR absorption bands for the structures of the (SiO2)n and (TiO2)n clusters are in good agreement with the bands observed in the IR spectra of the SiO2 and TiO2 films. It has been shown that the dissociative adsorption of the water occurs at the silicon centers, while the molecular form of adsorption is more energetically favorable at the active titanium centers. As a result of H2O adsorption, the electronic structure of TiO2 undergoes a transition from the semiconductor state to the dielectric one. The traces of water adsorbed at the titanium centers can be identified by the IR absorption spectra of samples due to a multiple (up to two orders of magnitude) increase in the intensities of the H2O molecule vibrations within the adsorption complex.

Lewis acid activated synthesis of highly substituted cyclopentanes by the N-heterocyclic carbene catalyzed addition of homoenolate equivalents to unsaturated ketoesters.

Lewis acid activated synthesis of highly substituted cyclopentanes by the N-heterocyclic carbene catalyzed addition of homoenolate equivalents to unsaturated ketoesters.

Novel heteroligated titanium complexes with fluorinated salicylaldiminato and β-enaminoketonato ligands: synthesis, characterization and catalytic behavior in vinyl addition polymerization of norbornene

A series of heteroligated (salicylaldiminato)(β-enaminoketonato)titanium complexes of the general formula [3-Bu(t)-2-OC(6)H(3)CH==N(C(6)F(5))][PhN==C(CF(3))CHC(R)O]TiCl(2) (3a: R==Ph, 3b: R==C(6)H(4)Ph(p), 3c: R==C(6)H(4)Ph(o), 3d: R = 1-naphthyl, 3e: R = C(6)H(4)F2(2,6), 3f: R = C(6)H(4)Cl2(2,5), 3g: R==C(6)F4(2,3,5,6)OMe(4)) were synthesized. The structure of complexes 3d, 3f-g were determined by single crystal X-ray diffraction analysis. The X-ray crystallographic analysis indicated these complexes adopted a distorted octahedral geometry around the titanium center. Upon activation with modified methylaluminoxane, complexes 3a-g exhibited moderate to good catalytic activity for norbornene (NB) vinyl addition polymerization, producing moderate molecular weight polynorbornenes under mild conditions. The introduction of electron-withdrawing groups can greatly enhance the catalytic activity. Significantly, the heteroligated titanium complexes displayed greatly improved activity for vinyl addition polymerization of NB compared to homoligated counterparts, which may stem from the suitable combinations of electronic and steric effects.

Mono N,C,N-pincer complexes of titanium, vanadium and niobium. Synthesis, structure and catalytic activity in olefin polymerisation

Transmetallation of 4,4'-bis{(2,6-bis[(dimethylamino)methyl]phenylgold)diphenyl-phosphino}biphenyl (3) with MCl(4) (M = Ti, NbCl, V) in benzene gave the corresponding transition metal pincer complexes (4) and insoluble 4,4'-bis[P-(chloro gold(I))diphenylphosphino]biphenyl (2), which can be quantitatively recovered and recycled. Interestingly, 3 did not react with TiCl(3). However, reaction of 2,6-bis[(dimethylamino)methyl]phenyllithium (1) with TiCl(3) resulted in formation of the novel diaryltitanium(IV) compound 5 (16% yield), comprising one N,C,N-mer bound NCN-pincer ligand and a second NCN-pincer ligand that is rearranged from a 1,2,6-isomer to a 1,2,4 one. The latter NCN-ligand is dianionic and is bidentate bonded; one of the CH(2)NMe(2) substituents (para to C'(ipso)) is non-coordinated, while the second CH(2)NMe(2) group, after C-H activation of one of the Me groups, is η(2)-C,N-bonded to the titanium centre trans to C(ipso) of the mer-NCN ligand. The new NCN-pincer metal complexes 2,6-bis[(dimethylamino)methyl]phenylTiCl(3) (4a) and 2,6-bis[(dimethylamino)methyl]-phenylVCl(2) (4d) gave, after immobilization on MgCl(2)-based supports, very high activity in ethene polymerisation.

Sr(ii)-UPRM-5 titanium silicate framework thermally induced contraction: in situ high temperature XRD and 29Si MAS NMR

The thermally induced contraction process of a titanosilicate prepared with tetraethylammonium hydroxide and ion exchanged with Sr(II) (Sr-UPRM-5) after detemplation has been characterized via in situ high temperature X-ray diffraction (XRD) and (29)Si magic angle spinning nuclear magnetic resonance (MAS NMR). The as-synthesized material was prepared via conventional and microwave-assisted hydrothermal methods, the latter resulting in a reaction time an order of magnitude shorter than the former case. In situ high temperature XRD tests performed on Sr-UPRM-5 indicate that at 120 °C, water coordinated to the structure is released initiating the collapse of the framework. At much higher temperatures, the material eventually becomes an amorphous phase. Indexing of the XRD patterns indicates that lattice constant a was more affected by the heat treatment, probably related to the material's pore system, while the unit cell volume experienced a 44% reduction. (29)Si MAS NMR analyses for as-synthesized UPRM-5 confirmed two different silicon environments: Si(2Si, 2Ti(octa)) and Si(3Si, 1Ti(semi-octa)), which are similar to those exhibited by titanosilicate ETS-4. On the other hand, in situ high temperature (29)Si MAS NMR analyses for Sr-UPRM-5 demonstrated that changes in the silicon environment due to the presence of titanium centers possessing additional multiple coordination states, which arise from elimination of framework coordinated water molecules, are responsible for the structure collapsing. In general, these results underline the importance of avoiding complete removal of tenacious water molecules in order to preserve the Sr-UPRM-5 properties suitable for adsorption and catalysis applications.

Computational Study of Silica-Supported Transition Metal Fragments for Kubas-type Hydrogen Storage

To verify the role of the Kubas interaction in transition metal grafted mesoporous silicas, and to rationalize unusual rising enthalpy trends with surface coverage by hydrogen in these systems, computational studies have been performed. Thus, the interaction of H2 with the titanium centers in molecular models for experimentally characterized mesoporous silica-based H2 absorption materials has been studied quantum chemically using gradient corrected density functional theory. The interaction between the titanium and the H2 molecules is found to be of a synergic, Kubas type, and a maximum of four H2 molecules can be bound to each titanium, in good agreement with previous experiments. The average Ti-H2 interaction energies in molecules incorporating benzyl ancillary ligands (models of the experimental systems) increase as the number of bound H2 units increases from two to four, in agreement with the experimental observation that the H2 adsorption enthalpy increases as the number of adsorbed H2 molecules increases. The Ti-H2 interaction is shown to be greater when the titanium is bound to ancillary ligands, which are poor π-acceptors, and when the ancillary ligand causes the least steric hindrance to the metal. Extension of the target systems to vanadium and chromium shows that, for molecules containing hydride ancillary ligands, a good relationship is found between the energies of the frontier molecular orbitals of the molecular fragments, which interact with incoming H2 molecules, and the strength of the M-H2 interaction. For the benzyl systems, both the differences in M-H2 interaction energies and the energy differences in frontier orbital energies are smaller than those in the hydrides, such that conclusions based on frontier orbital energies are less robust than for the hydride systems. Because of the high enthalpies predicted for organometallic fragments containing hydride ligands, and the low affinity of Cr(III) for hydrogen in this study, these features may not be ideal for a practical hydrogen storage system.

Synthesis and Reactivity of the Phospha‐Grignard Reagent Mg(P{SiMe3}2)Br(thf)

AbstractThe novel phospha‐Grignard reagent Mg(PR′2)X(thf) [R′ = SiMe3, X = Br (1)/Me (1′)] was synthesized and structurally characterized as the phosphide‐bridged dimer [1]2. The potential for this compound to behave as a redox‐friendly phosphide transfer reagent was probed by its reaction with group 4 metallocene compounds Cp2MCl2 (M = Ti, Zr), resulting in phosphide transfer to zirconium, but reduction of the titanium centre to TiIII.

On the Structure of Layered Double Hydroxides Intercalated with Titanium Tartrate Complex for Catalytic Asymmetric Sulfoxidation

Titanium tartrate complex has been intercalated within the gallery spaces of MΠ/Al layered double hydroxides (LDHs) (MII = Mg2+, Zn2+, Co2+) by ion exchange using CO32− LDHs as precursors. It is found that the intercalation hardly influences the coordination number of the titanium center while making tiny perturbation on the average Ti···O distances and octahedral symmetry. The complex anions are arranged in the interlayer gallery in an interdigitated bilayer with the coordinated carboxylates pointing to the brucite-like layer and the alkoxy group adjacent to the equivalent in another complex through hydrophobic interaction. The arrangement of interlayer titanium tartrate complex has been modulated by adjusting the charge density of unit brucite-like layer and the charge occupancy of the interlayer Ti(IV)TA2 anions. The intercalated structure is not collapsed until 573 K in the thermal treatment. The composition of the brucite-like layer as host hardly influences the bilayer arrangement of interlayer comp...

The Synthesis and Characterization of New, Robust Titanium (IV) Scorpionate Complexes

Titanium complexes possessing sterically encumbered ligands have allowed for the preparation of reactive moieties (imido, alkylidene and alkylidyne species) relevant to reactions such as olefin polymerization and alkyne hydroamination. For this reason, we have targeted robust scorpionate ancillary ligands to support reactive titanium centers. Thus, a series of titanium complexes were synthesized using an achiral oxazoline-based scorpionate ligand, tris(4,4-dimethyl-2-oxazolinyl)phenyl borate [To^M^]^-^ as well as the related chiral ligand, tris(4-isopropyl-2-oxazolinyl)phenyl borate [To^P^]^-^. The complex [Ti(κ^3^- To^M^)Cl~3~] was prepared in moderate yield (43%) by the rapid (<1 min at room temperature) reaction of Li[To^M^] and TiCl~4~ in methylene chloride; this new compound was characterized by ^1^H NMR spectroscopy as the expected C~3v~-symmetric species. One route to Ti (IV) alkyls involves salt metathesis; accordingly, syntheses of [To^M^]Ti alkyl complexes by interaction of [Ti(κ^3^-To^M^)Cl~3~] and one or three equivalents of alkylating agents, such as benzyl potassium (KCH~2~C~6~H~5~), trimethylsilylmethyllithium (LiCH~2~Si(CH~3~) ~3~), or neopentyl lithium (LiCH~2~C(CH~3~)~3~) are currently under investigation. The complexes [Ti(=NBut) (κ~3~-To^M^)(Cl)(Bu^t^py)] (Bu^t^py=4 tert-butylpyridine) and [Ti(=NBu^t^) (κ~3~-To^P^)(Cl)(Bu^t^py)] were synthesized by reaction of the known Ti imido [Ti(=NBu^t^)(Cl)~2~(Bu^t^py)~2~] with Li[To^M^] or Li[To^P^], respectively, by stirring overnight in methylene chloride at ambient temperature. The complexes were identified using ^1^H NMR spectroscopy, ^1^H-^13^C HMQC and ^1^H-^15^N HMBC correlation experiments.

The Synthesis and Characterization of New, Robust Titanium (IV) Scorpionate Complexes

AbstractTitanium complexes possessing sterically encumbered ligands have allowed for the preparation of reactive moieties (imido, alkylidene and alkylidyne species) relevant to reactions such as olefin polymerization and alkyne hydroamination. For this reason, we have targeted robust scorpionate ancillary ligands to support reactive titanium centers. Thus, a series of titanium complexes were synthesized using an achiral oxazoline-based scorpionate ligand, tris(4,4-dimethyl-2-oxazolinyl)phenyl borate [To^M^]^-^ as well as the related chiral ligand, tris(4-isopropyl-2-oxazolinyl)phenyl borate [To^P^]^-^. The complex [Ti(κ^3^- To^M^)Cl~3~] was prepared in moderate yield (43%) by the rapid (&lt;1 min at room temperature) reaction of Li[To^M^] and TiCl~4~ in methylene chloride; this new compound was characterized by ^1^H NMR spectroscopy as the expected C~3v~-symmetric species. One route to Ti (IV) alkyls involves salt metathesis; accordingly, syntheses of [To^M^]Ti alkyl complexes by interaction of [Ti(κ^3^-To^M^)Cl~3~] and one or three equivalents of alkylating agents, such as benzyl potassium (KCH~2~C~6~H~5~), trimethylsilylmethyllithium (LiCH~2~Si(CH~3~) ~3~), or neopentyl lithium (LiCH~2~C(CH~3~)~3~) are currently under investigation. The complexes [Ti(=NBut) (κ~3~-To^M^)(Cl)(Bu^t^py)] (Bu^t^py=4 tert-butylpyridine) and [Ti(=NBu^t^) (κ~3~-To^P^)(Cl)(Bu^t^py)] were synthesized by reaction of the known Ti imido [Ti(=NBu^t^)(Cl)~2~(Bu^t^py)~2~] with Li[To^M^] or Li[To^P^], respectively, by stirring overnight in methylene chloride at ambient temperature. The complexes were identified using ^1^H NMR spectroscopy, ^1^H-^13^C HMQC and ^1^H-^15^N HMBC correlation experiments.

Synthesis and Characterization of Titanium Mesoporous Silicate

In this project, surfactant hegzadesil three-methyl ammonium chloride was used as a structural informant or mould for synthesis of Mesoporous silicate molecular sieves. Many of the Mesoporous titanium silicates were synthesized by adding titanium compounds to the mixture, but considerable ratio of titanium centers placed in the frame are not accessible. This disadvantage was compensated by titanium butoxide as a titanous compound after being linked to the interior surfaces of host Mesoporous. The Mesoporous silicate was synthesized by, S+I− method, and then titanium was linked into the cavities. The structure of synthesized compound was characterized and studied by using XRD, XRF, TGA, SEM, IR techniques, and surface adsorption of nitrogen. The results showed the formation of meso structure with hexagonal cavities, high surface area, isomorphic cavities, spherical morphology, functional groups, and the amount of titanium input into the structure.

Synthesis, structure and ethylene (co)polymerization behavior of new nonbridged half-metallocene-type titanium complexes based on bidentate β-enaminoketonato ligands

A series of novel half-metallocene-type titanium complexes CpTiCl2[PhNC(R2)CHC(R1)O] (2a, R1 = Cy, R2 = CF3; 2b, R1 = tBu, R2 = CF3; 2c, R1 = Ph, R2 = CF3; 2d, R1 = Ph, R2 = CH3) have been synthesized by treating CpTiCl3 with the corresponding bidentate β-enaminoketonato ligands PhNC(R2)CHC(R1)OH in the presence of triethylamine. Single crystal X-ray diffraction revealed that complex 2b adopts distorted square-pyramid geometry around the titanium center. The complexes 2a–d were investigated as the catalysts for ethylene polymerization and the copolymerization of ethylene with norbornene. All the complexes were active towards ethylene (co)polymerization in the presence of modified methylaluminoxane, and produced high molecular weight (co)polymers. The catalytic activity and the norbornene incorporation were highly dependent upon catalyst and reaction conditions employed. Among four complexes, 2c exhibited both high catalytic activity and efficient norbornene incorporation under the same conditions, affording high molecular weight copolymers with unimodal molecular weight distributions.

Assembly of titanium embedded polyoxometalates with unprecedented structural features

Two titanium embedded polyoxometalates with unprecedented structural features are presented: a monotitanium containing tungstoantimonate Na(13)H(3)[TiO(SbW(9)O(33))(2)]·33 H(2)O featuring a {Ti=O}(2+) moiety (1) and a hexatitanium containing tungstoarsenate K(6)[Ti(4)(H(2)O)(10)(AsTiW(8)O(33))(2)]·30 H(2)O containing a {Ti(4)(H(2)O)(10)}(16+) moiety (2). Both compounds have been fully characterised by single crystal X-ray diffraction, elemental analysis, IR and TGA. 1 is constructed from two α-B-{Sb(III)W(9)O(33)} fragments linked by five sodium cations and an unprecedented square pyramidal Ti(O)O(4) group with a terminal Ti=O bond, and 2 exhibits a Krebs-type structure composed of two {AsTiW(8)O(33)} fragments, where one W(VI) centre has been substituted for a Ti(IV) centre in each, fused together via a belt of four additional Ti(IV) centres. This system represents the tungsten Ti-incorporated polyoxoanion with one of the highest Ti:W ratios so far reported. Additionally, 2 could also be isolated as an n-tetrabutylammonium salt and has been further characterised by electrochemistry and electrospray ionisation (ESI) MS studies. Due to the unique nature of these systems, both have been fully investigated using DFT calculations yielding highly interesting results. Structure 1 has been optimised with five sodium atoms in the belt position, which in addition to reducing the high charge of the cluster influence a stabilisation of the antimony lone pairs. Electrostatic potential calculations highlight the high electronegativity of the terminal oxygen on the titanium centre, enhancing real potentiality as a reactive site for catalysis.

Titanium complexes with sulfur-linked bis(phenolate) ligands

High-quality crystals of two bis(phenolate)titanium complexes, namely dichlorido{4,4'-dimethyl-2,2'-[cyclohexane-1,2-diylbis(sulfanediyl)]diphenolato}titanium(IV), [Ti(C(20)H(22)O(2)S(2))Cl(2)], (I), and dichlorido{2,2'-[cyclohexane-1,2-diylbis(sulfanediyl)]diphenolato}titanium(IV), [Ti(C(18)H(18)O(2)S(2))Cl(2)], (II), were obtained by reactive crystallization. Depending on the solvent, compound (II) was obtained as unsolvated (IIa) or as the toluene hemisolvate, [Ti(C(18)H(18)O(2)S(2))Cl(2)].0.5C(7)H(8), (IIb). These systems without bulky substituents on the aromatic phenolate rings serve as ideal model compounds for precatalysts. The excellent X-ray diffraction data will help clarify the nature of the mismatched interactions between the soft S atoms within the ligand and the hard titanium center. Molecule (I) has crystallographic C(2) symmetry.

Solid-State 49/47Ti NMR of Titanium-Based MCM-41 Hybrid Materials

Titanium solid-state NMR spectroscopy data for a series of organic-inorganic titanium MCM-41 based materials have been collected. These materials have been synthesized by first modifying the mesoporous silica MCM-41 in one step with a mixture of silanes: a triazine propyl triethoxysilane acting as functional linker and methyltrimethoxysilane or hexamethyldisilizane as capped agents to mask the remaining silanol groups. Second, the appropiate titanium precursor Ti(OPr(i))(4), [{Ti(OPr(i))(3)(OMent)}(2)] (OMent = 1R,2S,5R-(-)-menthoxo), Ti(OPr(i))(4), or [Ti(eta(5)-C(5)HMe(4))Cl(3)], has been immobilized by reaction with the modified MCM-41. Finally, after Ti(OPr(i))(4) immobilization onto the organomodified support the reaction with the chiral (+)-diethyl-l-tartrate was accomplished. The materials without functional linker have been also prepared by reaction in one step of the capped agent and the titanium precursor with the mesoporous silica. Relevant correlations of titanium NMR resonance chemical shifts and line widths can be inferred depending on different factors. The immobilization procedure used to prepare titanium-based MCM-41 hybrid materials and the choice of the silylating reagents employed to mask the silanol groups present on the silica surfaces produce significant differences in the Ti NMR spectra. Furthermore, depending on the electronic and sterical influence of the substituents directly attached to the titanium center, chemical shifts and line widths are modified providing novel information about titanium structure.

Tripodal Tetrahedral Titanium Coordination in the Silica-Grafted Titania Epoxidation Catalysts: Is Not It Only a Myth? Selective Formation of [Cy7Si7O12Ti]2(μ-OR)2(μ-ROH) Cores on Thermal “Dissociation” of Alkoxytitanasilsesquioxanes

The molecular structures of the species crystallizing from solutions of alkoxytitanasilsesquioxanes in hydrocarbons upon reflux confirm the partial release of solvating alcohol. They feature, however, distinctly the formation of a dinuclear core with preserved hexacoordination for the metal atoms. The active titanium centers in the silica-titania epoxidation catalysts, lacking the sterically demanding ligands, are thus quite probably also hexacoordinated.

Stereo- and enantioselective polymerization of hexa-1,5-diene on heterogeneous Ziegler-Natta catalysts obtained with the use of optically active internal donors

Pure racemates and individual enantiomers of diethyl 2,3-diisopropylsuccinate ((+,−)-DIPS and (−)-DIPS) and 2,3-diisopropyl-1,4-dimethoxybutane ((+,−)-DPDMB and (+)-DPDMB) were prepared. The synthesized compounds and diethyl phthalate were used as internal donors for the preparation of heterogeneous Ziegler-Natta catalysts. Polymerization of hexa-1,5-diene was carried out on these catalysts. The obtained samples of poly(methylene-1,3-cyclopentane) were studied by 13C NMR spectroscopy and polarimetry. The induction of optical activity to polymer is observed with (−)-DIPS as the internal donor. The induction value makes up 15–20% from the value recorded in the case of optically active metallocene catalysts. The emergence of induction may be associated with the presence of close contact between the titanium atom and the donor molecule within the active site of catalyst, as well as with the fact that the donor molecule either deactivates a part of the stereospecific titanium centers or influences the structure of the titanium centers during their formation and development.

2,2′-Bipyrrolidine versus 1,2-Diaminocyclohexane as Chiral Cores for Helically Wrapping Diamine−Diolate Ligands

The synthesis of chiral tetradentate dianionic diamine-diolate ligands assembled around either N,N'-dimethyl-trans-1,2-diaminocyclohexane or 2,2'-bipyrrolidine is described. These ligands wrap in a fac-fac helical mode around octahedral titanium and zirconium centers giving chiral-at-metal complexes. Diaminocyclohexane was found to be a poor chiral motif for diastereoselective helical wrapping, and all complexes of this family were obtained as mixtures of stereoisomers. In contrast, bipyrrolidine was found to be a perfect chiral motif for helical wrapping, and the corresponding diamine-diolate complexes were obtained as (enantiomerically pure) single diastereomers.

Reactions of Titanium Hydrazinediido Complexes with Unsaturated Organic Substrates

Reaction of [Cp*Ti(NXylN){N-NPh2}(NH2tBu)] (1a) with 1 molar equiv of phenylallene resulted in the formation of a mixture of the two metallacyclic compounds [Cp*Ti(NXylN){κ2N(NPh2)C(CHPh)CH2}] (2a and 2b) in a molar ratio of 3:1. Comparison of the 13C and 15N NMR resonances with the computed chemical shifts, along with an X-ray diffraction study of 2a, allowed the assignment of the diastereomers as the cycloadducts derived from a (3,2)-cycloaddition of the allene to the Ti═N bond. Upon reaction of 1a with phenylisothiocyanate, two complexes were formed in a 3:1 ratio. The major isomer, [Cp*Ti(NXylN){κ2-N(NPh2)C(NPh)S}] (4a), was isolated and identified by X-ray diffraction to result from a [2+2] cycloaddition of the C═S bond in PhNCS to the Ti═N bond of the hydrazinediido unit, giving a four-membered metallacyclic ring with an S,N-coordination to the titanium center and an exocyclic C═N double bond. In the minor compound (4b) the two nitrogen atoms of the thiourea unit formed in the cycloaddition are coordinated to the titanium center. Isomerization between the cycloadducts occurs only in the direction 4b → 4a, and crossover experiments indicate a dissociative mechanism (via a retro-cycloaddition) for the rearrangement. The reaction of 1a with PhNCO gave analogous N,O- and N,N-coordinated cycloadducts. Finally, the N,N-dimethyl hydrazinediido complexes reacted unspecifically with most organic azides at ambient temperature. However, complex [Cp*Ti(NXylN){N-NMe2}(dmap)] (1c) underwent a clean and fast reaction with trimethylsilylazide to give the N-silylated η2-hydrazido(1−) titanium azide [Cp*Ti(NXylN)(η2-NMe2-NSiMe3)(N3)] (8), in which the trimethylsilyl group of the azide is transferred to the hydrazido ligand, while the azide is terminally coordinated to the titanium center.