Formic acid modified Ti(OCHMe{sub 2}){sub 4}. Syntheses, characterization, and X-ray structures of Ti{sub 4}({mu}{sub 4}-O)({mu}-O)(OFc){sub 2}({mu}-OR){sub 4}(OR){sub 6} and Ti{sub 6}({mu}{sub 3}-O){sub 6}(OFc){sub 6}(OFc){sub 6}(OR){sub 6} (OFc = O{sub 2}CH; OR = OCHME{sub 2})
- Sandia National Labs., Albuquerque, NM (United States). Advanced Materials Lab.
- Los Alamos National Labs., NM (United States)
Novel structural arrangements for carboxylic acid modified titanium alkoxides were obtained from stoichiometric reactions between titanium isopropoxide (Ti(OPr{sup i}){sub 4}) and formic acid (HOFc). The 1:1 reaction in toluene forms the tetranuclear species Ti{sub 4}O{sub 2}(OFc){sub 2}(OPr{sup i}){sub 10}. 1. The structure of 1 was solved in the triclinic space group. The general structure of 1 resembles two face-shared [Ti-O]{sub 4} cubes with one set of mirror-related titanium atoms removed. The oxygen atoms are represented by one {mu}{sub 4}-O, one {mu}-O, and four {mu}-OR ligands, with the remaining sites filled by two OFc ligands and six terminal alkoxides. Increasing the stoichiometry to 1:2 (Ti/HOFc) leads to the isolation of Ti{sub 6}O{sub 6}(OFc){sub 6}(OR){sub 6}. 2. The structure of 2 was solved in the monoclinic space group. The structure of 2 consists of two offset six-membered [Ti-({mu}{sub 3}-O)]{sub 3} rings joined through Ti-O bonds. The OFc ligands are arranged externally around the central hexagon-prism, oscillating between the top and bottom rings. Compound 1 adopts a very symmetrical arrangement in solution due to the labile OFc ligands and was found to undergo aging by a trans-esterification mechanism, the rate of which is enhanced by heating. Compound 2 maintains its solid-state structure in solution.
- Research Organization:
- Sandia National Laboratory
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- AC04-94AL85000
- OSTI ID:
- 321103
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 21 Vol. 37; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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