Experimental and Theoretical Studies of Unusual Four‐Membered Metallacycles from Reactions of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes with the Sulfurdiimide Me<sub>3</sub>SiN=S=NSiMe<sub>3</sub>

Kaleta, Katharina; Ruhmann, Martin; Theilmann, Oliver; Roy, Sounak; Beweries, Torsten; Arndt, Perdita; Villinger, Alexander; Jemmis, Eluvathingal D.; Schulz, Axel; Rosenthal, Uwe

doi:10.1002/ejic.201101188

Cited by 23 publications

(32 citation statements)

References 38 publications

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“…Starting from different group 4 metallocene bis(trimethylsilyl)acetylene complexes Cp′ 2 M(L)(η 2 ‐btmsa) and neutral donor ligands by substitution of the alkyne a broad range of complexes was obtained . Sulfurdimides like 1,3‐ N , N′ ‐bis(trimethylsilyl)sulfurdimide react with Cp 2 M fragments (M = Ti, Zr) in this fashion, forming four‐membered heterometallacycles (Scheme ).…”

Section: Reactions With Neutral N‐donor Compoundsmentioning

confidence: 99%

Recent Synthetic and Catalytic Applications of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes

Rosenthal

2019

Eur J Inorg Chem

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With the 30 years old first example of a stable group 4 metallocene bis(trimethylsilyl)acetylene (btmsa) complex Cp2Ti(η2‐btmsa) a series of similar complexes like Cp′2M(η2‐btmsa) (M = Ti, Zr; Cp′ = Cp, Cp* as η5‐pentamethylcyclopentadienyl and Cp′2 = rac‐(ebthi) as rac‐1,2‐ethylene‐1,1′‐bis(η5‐tetrahydroindenyl) ) represent excellent sources for the generation of the very reactive coordinatively and electronically unsaturated complex fragments [Cp'2M], which were used in many synthetic and catalytic reactions. Examples for this were oresented in several papers and summarized in some reviews. In this update new reactions of group 4 metallocene bis(trimethylsilyl)acetylene complexes towards symmetrically and unsymmetrically α‐dihetero‐substituted alkynes, reactions with other alkynes, di‐ and polyynes to metallacyclopentadienes as well as the conversions of the formed products are summarized. Additionally, novel synthetic applications of the formed metallacyclopentadienes on the basis of the zirconocene bis(trimethylsilyl)acetylene complex Cp2Zr(py)(η2‐btmsa) are highlighted. Reactions with imines, neutral N‐donor ligands, E‐H compounds (E = N, O, P), molecular hydrogen, water, phosphino‐ and aminoboranes, E‐Cl compounds (E = C, P), disilylated germylenes and aryloxy ketones were described. Different self‐assembly reactions to multinuclear complexes by using group 4 metallocene bis(trimethylsilyl)acetylene complexes in C‐C coupling reactions with or without C‐H bond activation to tri‐ or tetranuclear complexes are considered, too. These examples are discussed following the general L‐M‐S principle for stoichiometric and catalytic reactions, whereby different ligands L (L = Cp′ = Cp, Cp*, rac‐ebthi), metals M (M = Ti, Zr, Hf) and substrate substituents S influence the reactivity and the obtained products.

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Section: Reactions With Neutral N‐donor Compoundsmentioning

confidence: 99%

Recent Synthetic and Catalytic Applications of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes

Rosenthal

2019

Eur J Inorg Chem

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“…30 The surface area of ligands and complexes were measured and presented in Table-1. Theoretical calculations studied by K. Kaleta et.al 39 and bands shifted to higher wavelength region depends on small dipoles groups present on the system. Therefore, Ti(DCMPPT)O exhibits good photocatalytic activity other than two complexes.…”

Section: Resultsmentioning

confidence: 94%

New photocatalyst for allylic aliphatic C–H bond activation and degradation of organic pollutants: Schiff base Ti(iv) complexes

et al. 2015

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The Schiff's base metal complexes have been concerned significantly due to their out-of-box applications in the environmental quantum leap by mineralization of the organic pollutants to fewer harmful byproducts and oxygen generation such as photosynthesis process. The Ti 4+ complexes obtained from Schiff base ligands reacted with donor atoms such as S and N under solvothermal conditions. These complexes were characterized using the microanalysis, conductivity studies, and different spectral techniques. From these data reveals that the compound shows distorted octahedral geometry with ligands coordination via azomethine nitrogen and thiol sulfur atoms. Oxidation of allylic methyl group examined the photocatalytic activity of [Ti(L)O] under ambient conditions and oxidative and cyclization under visible light irradiation. Ti(DCMPPT)O complex is very efficient catalyst due to the very short span of time convert aldehydes from allylic compounds. Aldehydes ready to react with 2-aminophenol or 2-aminobenzenethiol to produce (E)-2-styrylbenzo[d]oxazoles and (E)-2-styrylbenzo[d]thiazoles. Due to the suitable of the bandgap energy of nature to the generation of • OH radicals during the catalytic reaction. For this reason, higher oxidation rate. [Ti(DCMPPT)O] as a very efficient photocatalyst for degradation of MB, due large surface area and that supports to lower recombination energy mechanism.

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“…The titanium atom is coordinated by one pentamethylcyclopentadienyl ligand and a trimethylsilyl amino group and is part of a planar four-membered metallacycle (N1-Ti1-N3-S1 4.7°). [13] The sulfur atom adopts a distorted pseudotetrahedral geometry [N1-S1-N3 92.21(7)°, N1-S1-N2 108.54(8)°and N2-S1-N3 110.23(8)°]. Ti-N as well as N-S distances in the ring unit are equal and correspond to typical single bonds [Ti-N 1.938(2), N-S 1.703(2) Å].…”

Section: Resultsmentioning

confidence: 99%

“…[13] In this earlier paper, we re- Scheme ported on the unusual structure and bonding of this heterometallacycle by means of X-ray diffraction analysis and DFT calculations. [13] In this earlier paper, we re- Scheme ported on the unusual structure and bonding of this heterometallacycle by means of X-ray diffraction analysis and DFT calculations.…”

Section: Introductionmentioning

confidence: 99%

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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Experimental and Theoretical Studies of Unusual Four‐Membered Metallacycles from Reactions of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes with the Sulfurdiimide Me₃SiN=S=NSiMe₃

Cited by 23 publications

References 38 publications

Recent Synthetic and Catalytic Applications of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes

Recent Synthetic and Catalytic Applications of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes

New photocatalyst for allylic aliphatic C–H bond activation and degradation of organic pollutants: Schiff base Ti(iv) complexes

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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Experimental and Theoretical Studies of Unusual Four‐Membered Metallacycles from Reactions of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes with the Sulfurdiimide Me3SiN=S=NSiMe3

Cited by 23 publications

References 38 publications

Recent Synthetic and Catalytic Applications of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes

Recent Synthetic and Catalytic Applications of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes

New photocatalyst for allylic aliphatic C–H bond activation and degradation of organic pollutants: Schiff base Ti(iv) complexes

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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Experimental and Theoretical Studies of Unusual Four‐Membered Metallacycles from Reactions of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes with the Sulfurdiimide Me₃SiN=S=NSiMe₃

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