Highly selective visible light-induced Ti–O bond splitting in an ansa-titanocene dihydroxido complex

Godemann, Christian; Dura, Laura; Hollmann, Dirk; Grabow, Kathleen; Bentrup, Ursula; Jiao, Haijun; Schulz, Axel; Brückner, Angelika; Beweries, Torsten

doi:10.1039/c4cc09733e

Cited by 18 publications

(16 citation statements)

References 19 publications

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“…For ab etter understanding of the nature of complex 5,w e carried out EPR measurements at 27 8Ci nt oluenes olution, which clearly confirm the formation of as ingle d 1 titanium(III) complexw ith a g value of 1.9817 ( Figure 1). [18] In contrastt o this, the experimental data of 6 reveal unambiguously the formation of the 1-zircona(IV)-2-aza-5-oxa-cyclopent-3-ene, with no hints for an analogous paramagnetic zirconium(III) species. The complex formally consists of d 0 zirconocene(IV) and the dianionic [acpy] 2À ligand (see the Structure Discussion below).…”

Section: Reactionsof2 -Acetylpyridine (Acpy)mentioning

confidence: 85%

Reactions of 2‐Substituted Pyridines with Titanocenes and Zirconocenes: Coupling versus Dearomatisation

Reiß

Altenburger

Becker

et al. 2016

Chemistry A European J

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Reactions of group 4 metallocene sources with 2-substituted pyridines were investigated to evaluate their coordination type between innocent and reductive dearomatisation as well as to probe the possibility for couplings. A dependence on the cyclopentadienyl ligands (Cp, Cp*), the metals (Ti, Zr), and the substrates (2-phenyl-, 2-acetyl-, and 2-iminopyridine) was observed. While 2-phenylpyridine is barely reactive, 2-acetylpyridine reacts vigorously with the Cp-substituted complexes and selectively with their Cp* analogues. With 2-iminopyridine, in all cases selective reactions were observed. In the isolated [Cp Ti], [Cp Zr], and [Cp* Zr] compounds the substrate coordinates by its pyridyl ring and the unsaturated side-chain. Subsequently, the pyridine was dearomatised, which is most pronounced in the [Cp* Zr] compounds. Using [Cp* Ti] leads to the unexpected paramagnetic complexes [Cp* Ti (N,O-acpy)] and [Cp* Ti (N,N'-impy)]. This highlights the non-innocent character of the pyridyl substrates.

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Section: Reactionsof2 -Acetylpyridine (Acpy)mentioning

confidence: 85%

Reactions of 2‐Substituted Pyridines with Titanocenes and Zirconocenes: Coupling versus Dearomatisation

Reiß

Altenburger

Becker

et al. 2016

Chemistry A European J

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“…have been utilized for this purpose [6] . Concerning photohomolysis of Ti complexes, [7,8] cleavage of a Ti−OH bond in a well‐designed ligand [7b–d] or a Cp−Ti bond for initiation of radical polymerization [8] has been reported to date. However, photohomolytic generation of Ti(III) species has not yet been applied to catalytic C−C bond formation reactions.…”

Section: Methodsmentioning

confidence: 99%

Use of Isopropyl Alcohol as a Reductant for Catalytic Dehydoxylative Dimerization of Benzylic Alcohols Utilizing Ti−O Bond Photohomolysis

2021

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Photohomolysis of Ti−O bonds is utilized in photocatalytic generation of titanium(III) species for dehydroxylative dimerization of benzylic alcohols under UV‐light irradiation by using isopropyl alcohol (IPA) as a stoichiometric reductant. In this reaction, IPA works not as a single‐electron donor as in the photo‐redox catalyzed reactions but as an H‐atom‐donor. The reaction also proceeds under visible‐light irradiation in the presence of thioglycolic acid as a ligand.

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“…For synthesis of the title compound, see: Kessler et al (2013). For group 4 complexes with this ligand, see: Godemann et al (2014Godemann et al ( , 2015; Pinkas et al (2011); Xu et al (1997) Table 1 Hydrogen-bond geometry (Å , ).…”

Section: Related Literaturementioning

confidence: 99%

Crystal structure of 1,1,2,2-tetramethyl-1,2-bis(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)disilane

Godemann¹,

Spannenberg²,

Beweries³

2015

Acta Cryst E

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The molecular structure of the title compound, C22H38Si2, features a trans arrangement of the cyclopentadienyl rings to avoid steric strain [C—Si—Si—C torsion angle = −179.0 (5)°]. The Si—Si bond length is 2.3444 (4) Å. The most notable intermolecular interactions in the molecular packing are C—H⋯π contacts that lead to the formation of wave-like supramolecular chains along the b axis.

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Highly selective visible light-induced Ti–O bond splitting in an ansa-titanocene dihydroxido complex

Cited by 18 publications

References 19 publications

Reactions of 2‐Substituted Pyridines with Titanocenes and Zirconocenes: Coupling versus Dearomatisation

Reactions of 2‐Substituted Pyridines with Titanocenes and Zirconocenes: Coupling versus Dearomatisation

Use of Isopropyl Alcohol as a Reductant for Catalytic Dehydoxylative Dimerization of Benzylic Alcohols Utilizing Ti−O Bond Photohomolysis

Crystal structure of 1,1,2,2-tetramethyl-1,2-bis(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)disilane

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