Synthesis and Structure of Titanium(III) Bis(decamethyltitanocene) Oxide

0420871 - ÚFCH JH 2014 RIV US eng J - Journal Article
Pinkas, Jiří - Císařová, I. - Gyepes, Robert - Kubišta, Jiří - Horáček, Michal - Mach, Karel
Synthesis and Structure of Titanium(III) Bis(decamethyltitanocene) Oxide.
Organometallics. Roč. 32, č. 21 (2013), s. 6306-6314. ISSN 0276-7333. E-ISSN 1520-6041
R&D Projects: GA ČR(CZ) GAP207/12/2368; GA ČR GP203/09/P276
Institutional support: RVO:61388955
Keywords : BINUCLEAR DICYCLOPENTADIENYLTITANIUM(III) COMPLEXES * DICARBOXYLIC-ACID DIANIONS * X-RAY STRUCTURE
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 4.253, year: 2013

Bis(decamethyltitanocene) oxide, [(Cp*2Ti)2O] (1; Cp* = η5-C5Me5) has been obtained as a yellow crystalline solid after reacting equimolar amounts of the hydride [Cp*2TiH] and the hydroxide [Cp*2Ti(OH)]. The solid-state structure of 1 revealed a linear Ti−O−Ti arrangement and a mutual, nearly perpendicular orientation of the bent-sandwich titanocene moieties; the length of both Ti−O bonds amounted to 1.9080(3) Å. A unique structural feature was a close-to-eclipsed conformation of the cyclopentadienyl ligands, attributed to the high steric congestion of 1. The molecule in toluene glass exhibited a triplet state EPR spectrum of rhombic symmetry, having zero field splitting D = 0.02159 cm−1 and E = 0.00230 cm−1. The 1H NMR spectrum of 1 in toluene-d8 displays a paramagnetic resonance at δ 4.3 ppm (Δν1/2 ≈ 270 Hz). Compound 1 reacts with 1 molar equiv of water to give [Cp*2Ti(OH)]. In CD2Cl2, 1 is oxidized to yield the major product [(Cp*TiCl2)2O] and minor product [{Cp*Ti(Cl)O}3].
Permanent Link: http://hdl.handle.net/11104/0227399