Characterization of the Titanium(III) Tris(alkyl) Ti{CH(SiMe 3 ) 2 } 3 and its Conversion to a Dimeric Alkyl-Bridged Titanium(IV) Species.

Authors :: McLoughlin CP
Witt AJ
Maijala A
Shiau AA
Rao G
David Britt R
Tuononen HM
Power PP
Source :: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2025 Jan 19, pp. e202404696. Date of Electronic Publication: 2025 Jan 19.
Publication Year :: 2025
Publisher :: Ahead of Print
Abstract: The reaction of three equivalents of LiCH(SiMe <subscript>3</subscript> ) <subscript>2</subscript> with TiCl <subscript>3</subscript> (NMe <subscript>3</subscript> ) <subscript>2</subscript> afforded the rare homoleptic Ti(III) alkyl Ti{CH(SiMe <subscript>3</subscript> ) <subscript>2</subscript> } <subscript>3</subscript> (1) which crystallized as blue needles in 32 % yield. Single crystal X-Ray data for 1 showed a trigonal pyramidal coordination geometry around titanium, which could be ascribed to weak interactions between the C-H bonds and the Ti(III) atom based on computational results. X-band EPR spectroscopy gives spectral parameters consistent with the proposed Ti(III) formulation. Solutions of 1 are unstable at room temperature owing to intramolecular C-H activation that gave a dimeric Ti(IV) complex [{(Me <subscript>3</subscript> Si) <subscript>2</subscript> HC}Ti{μ-CHSiMe <subscript>2</subscript> CHSiMe <subscript>3</subscript> }] <subscript>2</subscript> (2).<br /> (© 2025 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

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