ic5002545_si_002.cif (2.44 MB)
The Structural Conversion of Multinuclear Titanium(IV) μ-Oxo-complexes
dataset
posted on 2014-10-20, 00:00 authored by Aleksandra Radtke, Piotr Piszczek, Tadeusz Muzioł, Andrzej WojtczakFor
the first time we report the structural conversion processes of hexanuclear
μ-oxo-Ti(IV) complexes into tetranuclear ones. Single-crystal
X-ray diffraction studies reveal that metastable hexanuclear μ-oxo
complexes ([Ti6O6(OtBu)(O2CR′)6]) are formed in the first
stage of reactions between [Ti(OtBu)4] and branched carboxylic acids R′COOH (R′ =
C(Me)2Et, CH2tBu, tBu). In the next stage they convert into
tetranuclear μ-oxo-Ti(IV) complexes of the formula [Ti4O4(OtBu)4(O2CR′)4]. Spectroscopic investigations (13C NMR, IR, and MS) proved that the conversion of hexanuclear
clusters relies on the attachment of smaller units (e.g., [Ti3O(OtBu)8(O2CR′)2] or [Ti4O2(OtBu)6(O2CR′)6]) and intermediate species formation (e.g., [Ti9O8(OtBu)14(O2CR′)6]). The decomposition of intermediate systems
in the next reaction stage leads to the formation of tetranuclear
clusters. The type of solvent used in the synthesis of multinuclear
oxo-Ti(IV) complexes is an important factor, which influences the
kind of clusters formed.