Photoassisted TiO Activation in a Decamethyltitanocene Dihydroxido Complex: Insights into the Elemental Steps of Water Splitting

Kessler, Monty; Schüler, Stefanie; Hollmann, Dirk; Klahn, Marcus; Beweries, Torsten; Spannenberg, Anke; Brückner, Angelika; Rosenthal, Uwe

doi:10.1002/anie.201202097

Cited by 34 publications

(33 citation statements)

References 32 publications

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“…We suppose that by the reaction of 15 a with 13 , the Cp* ligand is eliminated and the O atom transferred to the titanium. Subsequent to this, a complex could be formed, which might resemble the tetrameric [(Cp*Ti) 4 O 6 ] . Unfortunately, we were not able to isolate and characterise this new compound in detail.…”

Section: Resultsmentioning

confidence: 99%

Reactivity Study of Pyridyl‐Substituted 1‐Metalla‐2,5‐diaza‐cyclopenta‐2,4‐dienes of Group 4 Metallocenes

Becker

Reiß

Altenburger

et al. 2016

Chemistry A European J

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In this work the reactivity of 1-metalla-2,5-diaza-cyclopenta-2,4-dienes of group 4 metallocenes, especially of the pyridyl-substituted examples, towards small molecules is investigated. The addition of H2 , CO2 , Ph-C≡N, 2-py-C≡N, 1,3-dicyanobenzene or 2,6-dicyanopyridine results in exchange reactions, which are accompanied by the elimination of a nitrile. For CO2 , a coordination to the five-membered cycle occurs in case of Cp*2 Zr(N=C(2-py)-C(2-py)=N). A 1,4-diaza-buta-1,3-diene complex is formed by H-transfer in the conversion of the analogous titanocene compound with CH3 -C≡N, PhCH2 -C≡N or acetone. For CH3 -C≡N a coupling product of three acetonitrile molecules is established additionally. In order to split off the metallocene from the coupled nitriles, we examined reactions with HCl, PhPCl2 , PhPSCl2 and SOCl2 . In the last case, the respective thiadiazole oxides and the metallocene dichlorides were obtained. A subsequent reaction produced thiadiazoles.

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Section: Resultsmentioning

confidence: 99%

Reactivity Study of Pyridyl‐Substituted 1‐Metalla‐2,5‐diaza‐cyclopenta‐2,4‐dienes of Group 4 Metallocenes

Becker

Reiß

Altenburger

et al. 2016

Chemistry A European J

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“…Irradiation of a solution of this complex in n-hexane results in the formation of several well-defined mononuclear and tetranuclear Ti(III) and Ti(IV) complexes (e.g., 50 and 51) (Kessler et al 2012). The overall reaction most likely takes place via two different reaction pathways, namely by Ti-O bond activation and Cp* radical elimination (Scheme 14).…”

Section: Mechanistic Studies Of the Catalytic Cyclementioning

confidence: 99%

Organometallic water splitting – from coordination chemistry to catalysis

Klahn

Beweries

2014

Reviews in Inorganic Chemistry

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AbstractThis review gives an overview on the recent developments in the field of coordination chemistry of water at transition metal centres, which could give implications for a better understanding of the elementary steps of light-driven overall water splitting. Additionally, selected examples for homogeneous catalyst systems that are capable of producing hydrogen and/or oxygen from water are presented, focussing on the mechanistic aspects of water reduction and water oxidation.

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“…Evidently, in these reactions [Cp* 2 Ti] is less stable than [Cp 2 Ti]; a possible reason was found to be the well-known intramolecular C-H activation yielding the tautomeric tetramethylfulvene hydride species, from which 1,2,3,4-tetramethylfulvene (3) can dissociate. [12] Pentamethylcyclopentadienol and pentamethylcyclopentadiene, formed by recombination of Cp* · with OH · and H · (which were also cleaved off during irradiation), respectively, were found to be the organic products in this bond activation reaction. However, some examples of the activation or elimination of the cyclopentadienyl ligand were observed.…”

Section: Introductionmentioning

confidence: 96%

Different Inertness of Titanocene [Cp₂Ti] and Decamethyltitanocene [Cp*₂Ti] in Reactions with N,N‐Bis(trimethylsilyl)sulfurdiimide – Elimination of Tetramethylfulvene and Formation of Half‐Titanocene Complexes

et al. 2012

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The reaction of the titanocene alkyne complex [Cp*2Ti(η2‐Me3SiC2SiMe3)] (1) (Cp* = η5‐pentamethylcyclopentadienyl) with N,N‐bis(trimethylsilyl)sulfurdiimide (2) results in the formation of 1,2,3,4‐tetramethylfulvene (3) as well as three titanium complexes 4, 5 and 6. During the reaction, formal elimination of one Cp* ligand induces a series of C–H and N–S bond activation steps, thus yielding the products. The molecular structures of complex 5 and of the free fulvene were determined by X‐ray crystallographic analysis. Evidently, in these reactions [Cp*2Ti] is less stable than [Cp2Ti]; a possible reason was found to be the well‐known intramolecular C–H activation yielding the tautomeric tetramethylfulvene hydride species, from which 1,2,3,4‐tetramethylfulvene (3) can dissociate.

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Photoassisted TiO Activation in a Decamethyltitanocene Dihydroxido Complex: Insights into the Elemental Steps of Water Splitting

Cited by 34 publications

References 32 publications

Reactivity Study of Pyridyl‐Substituted 1‐Metalla‐2,5‐diaza‐cyclopenta‐2,4‐dienes of Group 4 Metallocenes

Reactivity Study of Pyridyl‐Substituted 1‐Metalla‐2,5‐diaza‐cyclopenta‐2,4‐dienes of Group 4 Metallocenes

Organometallic water splitting – from coordination chemistry to catalysis

Different Inertness of Titanocene [Cp₂Ti] and Decamethyltitanocene [Cp*₂Ti] in Reactions with N,N‐Bis(trimethylsilyl)sulfurdiimide – Elimination of Tetramethylfulvene and Formation of Half‐Titanocene Complexes

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Photoassisted TiO Activation in a Decamethyltitanocene Dihydroxido Complex: Insights into the Elemental Steps of Water Splitting

Cited by 34 publications

References 32 publications

Reactivity Study of Pyridyl‐Substituted 1‐Metalla‐2,5‐diaza‐cyclopenta‐2,4‐dienes of Group 4 Metallocenes

Reactivity Study of Pyridyl‐Substituted 1‐Metalla‐2,5‐diaza‐cyclopenta‐2,4‐dienes of Group 4 Metallocenes

Organometallic water splitting – from coordination chemistry to catalysis

Different Inertness of Titanocene [Cp2Ti] and Decamethyltitanocene [Cp*2Ti] in Reactions with N,N‐Bis(trimethylsilyl)sulfurdiimide – Elimination of Tetramethyl­fulvene and Formation of Half‐Titanocene Complexes

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Different Inertness of Titanocene [Cp₂Ti] and Decamethyltitanocene [Cp*₂Ti] in Reactions with N,N‐Bis(trimethylsilyl)sulfurdiimide – Elimination of Tetramethylfulvene and Formation of Half‐Titanocene Complexes