[Cp2TiCH2CH2(SiEt2CHMe2)]+, an Alkyl-titanocene(IV) Complex Containing an Unconventional Ti←C(β)-Si Mode of Bonding | Zendy

Alexandre F. Dunlop-Brière | Zendy; Michael C. Baird | Zendy; Peter H. M. Budzelaar | Zendy

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[Cp₂TiCH₂CH₂(SiEt₂CHMe₂)]⁺, an Alkyl-titanocene(IV) Complex Containing an Unconventional Ti←C(β)-Si Mode of Bonding

Author(s) -

Alexandre F. Dunlop-Brière,

Michael C. Baird,

Peter H. M. Budzelaar

Publication year - 2015

Publication title -

organometallics

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.231

H-Index - 172

eISSN - 1520-6041

pISSN - 0276-7333

DOI - 10.1021/acs.organomet.5b00675

Subject(s) - agostic interaction , chemistry , isomerization , metathesis , alkyl , intramolecular force , stereochemistry , metallocene , salt metathesis reaction , silylation , crystallography , medicinal chemistry , catalysis , organic chemistry , polymerization , polymer , metal

The compound [Cp2Ti(Me)(CD2Cl2)][B(C6F5)4] reacts with triethylvinylsilane (TEVS) to give the γ-agostic σ-alkyl complex [Cp2TiCH2CHMe(SiEt3)]+ (IV),\udthe product of a single 1,2-insertion of TEVS into the Ti-Me bond. On heating, complex IV undergoes a CH bond activation process to give the isomeric species [Cp2TiCH2CH2(SiEt2CHMe2)]+ (V) in which a Ti−C(β) interaction (Ti←C(β)-Si) is facilitated by an unusual γ-silyl effect. The structures of IV and V and the nature of the isomerization process were explored by DFT methods which suggest that isomerization proceeds via an intramolecular 1,5-σ bond metathesis reaction which involves ε-agostic interactions

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