The reaction of iron carboxylates with titanium alkoxides. Isolation and structural characterisation of [Ti 6(μ 3-O) 6(O 2CPh) 6(OCH 2C(CH 3) 3) 6]

• Published in: Inorganica Chimica Acta 2003-09, Vol.353, p.75-81
• Main Authors: Ammala, Paul S, Batten, Stuart R, Kepert, Christopher M, Spiccia, Leone, van den Bergen, Adrian M, West, Bruce O
• Format: Article
• Language: English
• Subjects: Fe carboxylates; Hexanuclear Ti-oxo-carboxylato-alkoxide; Ti alkoxides; X-ray structures
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/S0020-1693(03)00242-1

The reaction of [Fe 4(μ 3-O) 2(O 2CPh) 8(py) 2] ( 1) with Ti(OPr n ) 4 in toluene yields separate Fe and Ti species each containing both carboxylate and alkoxide groups rather than a bimetallic FeTi complex. The addition of neopentanol to the reaction mixture has enabled [Ti 6(μ 3-O) 6(O 2CPh) 6(OCH 2C(CH 3) 3) 6] ( 3) to be isolated and structurally identified. The compound [Ti 6(μ 3-O) 4(O 2CPh) 8(OPr n ) 8] ( 4) has also been characterised and shown not to convert to a {Ti 6(μ 3-O) 6} 12+ core compound under the same temperature conditions used in the FeTi reactions. Addition of neopentanol to a mixture obtained by refluxing [Fe 4(μ 3-O) 2(O 2CPh) 8(py) 2] ( 1) and Ti(OPr n ) 4 in toluene has led to the isolation and crystallographic identification of an oxo-Ti species, [Ti 6(μ 3-O) 6(O 2CPh) 6(OCH 2C(CH 3) 3) 6] ( 3) rather than an FeTi complex. Direct reaction of Ti(OPr n ) 4 and benzoic acid in toluene forms [Ti 6(μ 3-O) 4(O 2CPh) 8(OPr n ) 8] ( 4) which did not convert to a {Ti 6(μ 3-O) 6} 12+ core complex on prolonged heating.