Extending the family of titanium heterometallic-oxo-alkoxy cages

S Eslava, B.P.R. Goodwill, M. McPartlin, D.S. Wright

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Abstract

Here we investigate the synthesis of high-nuclearity heterometallic titanium oxo-alkoxy cages using the reactions of metal chlorides with [Ti(OEt) ] or the pre-formed homometallic titanium-oxo-alkoxy cage [Ti O (OEt) ] (A). The octanuclear Ti Co cage [Ti CoO (OEt) Cl] (1) (whose low-yielding synthesis we reported earlier) can be made in better yield, reproducibly by the reaction of a mixture of heptanuclear [Ti O (OEt) ] (A) and [KOEt] with [Co Cl ] in toluene. A alone reacts with [Co Cl ] and [Fe Cl ] to form [Ti Co O (OEt) Cl ] (2) and [Ti Fe O (OEt) Cl ] (3), respectively. Like 1, compounds 2 and 3 retain the original Ti fragment of A and the II-oxidation state of the transition metal ions (Tm). In contrast, from the reaction of [Ti(OEt) ] with [Cr Cl ] it is possible to isolate [Ti Cr O(OEt) Cl] (4) in low yield, containing a Ti Cr core in which oxidation of Cr from the II to V oxidation state has occurred. Reaction of [Mo Cl ] with [Ti(OEt)] in [EtOH] gives the Ti Mo cage [{Ti Mo O (OEt) } ] (5). The single-crystal X-ray structures of the new cages 2, 3, 4, and 5 are reported. The results show that the size of the heterometallic cage formed can be influenced by the nuclearity of the precursor. In the case of 5, the presence of homometallic Mo-Mo bonding also appears to be a significant factor in the final structure.
LanguageEnglish
Pages5655-5662
Number of pages8
JournalInorganic Chemistry
Volume50
Issue number12
DOIs
StatusPublished - 20 Jun 2011

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Titanium
titanium
Oxidation
oxidation
Toluene
Transition metals
Metal ions
Chlorides
synthesis
Metals
Single crystals
toluene
X rays
metal ions
transition metals
chlorides
fragments
alkoxyl radical
single crystals
metals

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Eslava, S., Goodwill, B. P. R., McPartlin, M., & Wright, D. S. (2011). Extending the family of titanium heterometallic-oxo-alkoxy cages. Inorganic Chemistry, 50(12), 5655-5662. https://doi.org/10.1021/ic200350j

Extending the family of titanium heterometallic-oxo-alkoxy cages. / Eslava, S; Goodwill, B.P.R.; McPartlin, M.; Wright, D.S.

In: Inorganic Chemistry, Vol. 50, No. 12, 20.06.2011, p. 5655-5662.

Research output: Contribution to journalArticle

Eslava, S, Goodwill, BPR, McPartlin, M & Wright, DS 2011, 'Extending the family of titanium heterometallic-oxo-alkoxy cages' Inorganic Chemistry, vol. 50, no. 12, pp. 5655-5662. https://doi.org/10.1021/ic200350j
Eslava, S ; Goodwill, B.P.R. ; McPartlin, M. ; Wright, D.S. / Extending the family of titanium heterometallic-oxo-alkoxy cages. In: Inorganic Chemistry. 2011 ; Vol. 50, No. 12. pp. 5655-5662.
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AB - Here we investigate the synthesis of high-nuclearity heterometallic titanium oxo-alkoxy cages using the reactions of metal chlorides with [Ti(OEt) ] or the pre-formed homometallic titanium-oxo-alkoxy cage [Ti O (OEt) ] (A). The octanuclear Ti Co cage [Ti CoO (OEt) Cl] (1) (whose low-yielding synthesis we reported earlier) can be made in better yield, reproducibly by the reaction of a mixture of heptanuclear [Ti O (OEt) ] (A) and [KOEt] with [Co Cl ] in toluene. A alone reacts with [Co Cl ] and [Fe Cl ] to form [Ti Co O (OEt) Cl ] (2) and [Ti Fe O (OEt) Cl ] (3), respectively. Like 1, compounds 2 and 3 retain the original Ti fragment of A and the II-oxidation state of the transition metal ions (Tm). In contrast, from the reaction of [Ti(OEt) ] with [Cr Cl ] it is possible to isolate [Ti Cr O(OEt) Cl] (4) in low yield, containing a Ti Cr core in which oxidation of Cr from the II to V oxidation state has occurred. Reaction of [Mo Cl ] with [Ti(OEt)] in [EtOH] gives the Ti Mo cage [{Ti Mo O (OEt) } ] (5). The single-crystal X-ray structures of the new cages 2, 3, 4, and 5 are reported. The results show that the size of the heterometallic cage formed can be influenced by the nuclearity of the precursor. In the case of 5, the presence of homometallic Mo-Mo bonding also appears to be a significant factor in the final structure.

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