Molecular structure of (.eta.5-C5H5)2Ti(OC2H5)Cl and [(.eta.5-C5H5)Cl2Ti]2O2C2(CH3)4. A structural basis for deoxygenation using titanium

Huffman, John C.; Moloy, Kenneth G.; Marsella, John A.; Caulton, Kenneth G.

doi:10.1021/ja00529a022

Cited by 138 publications

(63 citation statements)

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“…While the latter distance is identical to that found in 6, these are significantly shorter than the Ti-0 distance seen in Cp2TiC1(OEt) (1.855(2) A) (8). This is con- The structure of 4 was confirmed by an X-ray crystallographic study (Fig.…”

Section: Structural Studiessupporting

confidence: 56%

“…Caulton and co-workers (8,9,11) have studied the formation of 6 from the reaction of 7 and CpTiCl, and suggest that destabilizing steric interactions between the methyl substituents of the pinacolate and the cyclopentadienyl ring are the driving force for the reaction. Similarly, we suggest that a mononuclear diolate species 9 (Scheme 1) is formed initially in the present reactions and that ligand redistribution reactions in the presence of CpTiCl, yield the products 1-3.…”

Section: Discussionmentioning

confidence: 99%

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Synthesis and structure of titanium diolate complexes derived from CpTiCl₃

Huang¹,

Stephan²

1995

Can. J. Chem.

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The compounds [C1,CpTi],(0CH2CH,CH,0) 1, [Cl,CpTi],(OCH,CMe,CH@) 2, and [CI,CpTi],-(OCHMeCH,CHMeO) 3 were prepared from the reactions of CpTiCl, and the bis-trimethylsilyl ethers of the diols. Alternatively, these species could be made from the reactions of the diol, imidazole, and CpTiCl, employing the appropriate stoichiometry. In the presence of excess diol, loss of CpH is observed. In the case of

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Section: Structural Studiessupporting

confidence: 56%

Section: Discussionmentioning

confidence: 99%

Synthesis and structure of titanium diolate complexes derived from CpTiCl₃

Huang¹,

Stephan²

1995

Can. J. Chem.

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“…The two Ti --angles in 1 were found to be 146.4(9) and 148.0(9)". These angles are significantly larger than that of 133.2(2)" found in Cp2Ti(OEt)C1 (12) and significantly smaller than that of 166.2(2)" found in [CpTiC120CMe212 (12). These variations in the Tiangles are consistent with the expected variations in T i 4 d n -p~ multiple bond character based on metal Lewis acidity considerations.…”

Section: Structural Studysupporting

confidence: 71%

“…The T i 4 bond distances in 1 are 1.80(1) and 1.82(1) A. These compare with Ti-0 distances of 1.855(2) and 1,750(2) A found in Cp2Ti(OEt)C1 and [CpTiC120CMe2]2, respectively ( 12). The two Ti --angles in 1 were found to be 146.4(9) and 148.0(9)".…”

Section: Structural Studysupporting

confidence: 55%

Bimetallic titanium alkoxides: synthesis and structure of Cp₂Ti(Ph)(μ-OCH₂C(CH₃)₂CH₂O)(Ph)TiCp₂; a precursor to macrocyclic metallocene derivatives

Nadasdi¹,

Stephan²

1991

Can. J. Chem.

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The reaction of Cp2TiPh2 with 2,2-dimethylpropane-1,3-diol proceeds with the evolution of benzene affording the bimetallic titanocene alkoxide species Cp2Ti(Ph)(p-OCH2C(CH3)2CH20)(Ph)TiCpz, 1. Complex 1 crystallizes in the monclinic space group Cc with a = 25.448(7) A, b = 8.483(s) A, c = 14.512(3) A, P = 101.52(2)", Z = 4, and V = 3070(1) A3. The structure was refined employing 1471 data with Fo > 3uF0 and 138 variables to R values of R = 0.0588 and R,,, = 0.0828. the dimeric nature of 1 is confirmed. The coordination spheres of the two Ti centres are pseudo-tetrahedral. The T i 4 u bonds were found to be 2.21(1) and 2.25(1) A. Although the phenyl substituents are directed towards each other, steric effects appear to be overcome by the approximately perpendicular orientation of the phenyl rings (in fact the angle between the planes is 81.9"). The Ti ... Ti separation in 1 is 6.725 A. The implications of the preparation of 1 regarding the mechanism of formation of early metal macrocyclic compounds are discussed. In addition, the ramifications for the synthesis of dissymmetric early metal macrocycles are considered.Key words: titanium alkoxides, alkoxide bridged, structure. Introduction Titania or zirconia are often employed as support materials for heterogeneous catalysts (1). These supports may act simply as a dispersent for the late metal centers or may play an active role in the catalytic cycle. In the latter case, such participation gives rise to the phenomenon known as strong metal-support interactions (SMSI) (1). Activation of substrate molecules by a Lewis acidic, early metal and a late metal center may account for the observed effects. We and others have investigated homogeneous systems in which early and late metals are linked in close proximity by bridging Iigands (2). Such heterobimetallics are of interest both as models for the heterogeneous catalyst systems and because of their potential as catalysts in their own right. Fewer studies have focused on simple complexes of Ti or Zr that might model the Lewis acidic, early metal centers of titania or zirconia. Several groups (3-3, have reported the syntheses and reaction chemistry of a variety of early metal alkoxide complexes. The similarity of metal-alkoxide species to metal oxides and the propriety of such species as models for metal-oxide surfaces have been considered by others (3). Much of the work to date has focused on systems in which sterically demanding alkoxy or aryloxy ligands inhibit oligomerization and yield mononuclear early metal compounds (4, 5). In our 'A complete set of supplementary material may be purchased from the Depository of Unpublished Data, CISTI, National Research Council of Canada, Ottawa, Ont., Canada KIA 0S2. initial investigations in this area, we described the specific formation of bimetallic macrocyclic Zr-alkoxide species via the reaction of dimethylzirconocene with diols (Scheme 1) (6).In this report we describe the product of the related reaction of Cp2TiPh2 with 2,2-dimethylpropanediol, i.e., Cp2Ti(Ph)(p-0CH2C(CH3)2...

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“…The most significant features of the structures are the long Ti(1)-O(6) bond lengths of 2b (1.931(2) Å ), 4b (1.921(3) Å ) and 6b (1.901(6) Å ), compared to that of typical terminal titanium(IV) alkoxides (1.855 Å in [TiCp 2 (OEt)Cl]. 20 The very short C(6)-O(6) bond distances of these complexes (1.279(4), 1.280(5) and 1.273(11) Å , respectively), as well as the near-linear bond angles for C(6)-O(6)-Ti(1) (171.7(3), 174.6(3) and 175.4(7)…”

Section: Molecular Structuresmentioning

confidence: 99%

Multimetal Fischer carbene complexes of Group VI transition metals: synthesis, structure and substituent effect investigation

et al. 2011

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Fischer carbene complexes of tungsten with substituents containing up to two additional different transition metals, with all the metals in electronic contact with the carbene carbon atom, were synthesised and studied both in solution and in the solid state. For the complexes of the type [W(CO) 5 {C(OR¢)R}], the substituents chosen were heteroaromatic 2-benzo[b]thienyl (2-BT), or 2-BT p-bonded to a chromium tricarbonyl fragment ([Cr(CO) 3 (2-h 6 -BT)]) or ferrocenyl (Fc) as the R-substituent, while the OR¢-substituent was systematically varied between an ethoxy or a titanoxy group, to yield the complexes 1b (R¢ = Et, R = 2-BT), 2b (R¢ = Et, R = [Cr(CO) 3 (2-h 6 -BT)]), 3b (R¢ = TiCp 2 Cl, R = 21-BT), 4b (R¢ = TiCp 2 Cl, R = [Cr(CO) 3 (2-h 6 -BT)]), 5b (R¢ = Et, R = Fc) and 6b (R¢ = TiCp 2 Cl, R = Fc). The structural features and their relevance to bonding in the multimetal carbene compounds of both these tungsten and the analogous chromium complexes were investigated as they represent indicators of possible reactivity sites in multimetal carbene assemblies. The possibility of using DFT calculations to quantify the effect of metal-containing substituents on the carbene ligands was tested and correlated with experimental parameters by employing methods such as vibrational spectroscopy, molecular orbital analysis, and cyclic voltammetry.

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Molecular structure of (.eta.5-C5H5)2Ti(OC2H5)Cl and [(.eta.5-C5H5)Cl2Ti]2O2C2(CH3)4. A structural basis for deoxygenation using titanium

Cited by 138 publications

References 5 publications

Synthesis and structure of titanium diolate complexes derived from CpTiCl₃

Synthesis and structure of titanium diolate complexes derived from CpTiCl₃

Bimetallic titanium alkoxides: synthesis and structure of Cp₂Ti(Ph)(μ-OCH₂C(CH₃)₂CH₂O)(Ph)TiCp₂; a precursor to macrocyclic metallocene derivatives

Multimetal Fischer carbene complexes of Group VI transition metals: synthesis, structure and substituent effect investigation

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Molecular structure of (.eta.5-C5H5)2Ti(OC2H5)Cl and [(.eta.5-C5H5)Cl2Ti]2O2C2(CH3)4. A structural basis for deoxygenation using titanium

Cited by 138 publications

References 5 publications

Synthesis and structure of titanium diolate complexes derived from CpTiCl3

Synthesis and structure of titanium diolate complexes derived from CpTiCl3

Bimetallic titanium alkoxides: synthesis and structure of Cp2Ti(Ph)(μ-OCH2C(CH3)2CH2O)(Ph)TiCp2; a precursor to macrocyclic metallocene derivatives

Multimetal Fischer carbene complexes of Group VI transition metals: synthesis, structure and substituent effect investigation

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Synthesis and structure of titanium diolate complexes derived from CpTiCl₃

Synthesis and structure of titanium diolate complexes derived from CpTiCl₃

Bimetallic titanium alkoxides: synthesis and structure of Cp₂Ti(Ph)(μ-OCH₂C(CH₃)₂CH₂O)(Ph)TiCp₂; a precursor to macrocyclic metallocene derivatives