Di-tert-butyl phosphate complexes of titanium
- Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
Reactions of 1 equiv of HO(O)P(O{sup 1}Bu){sub 2} with Ti(OR){sub 4} (R = Et, {sup i}Pr) give the new molecular titanium phosphates [Ti(OR){sub 3}O{sub 2}P(O{sup t}Bu){sub 2}]{sub n} (1, R = Et; 2, R = {sup i}Pr). In the solid state, 2 exists as a centrosymmetric dimer containing five-coordinate metal centers. Addition of 2 equiv of KOEt to an ethanol solution of 1 led to the formation of [Ti{sub 2}K(OEt){sub 8}O{sub 2}(O{sup t}Bu){sub 2}]{sub 2} (3) and 1 equiv of KO{sub 2}P(O{sup t}Bu){sub 2}. A single-crystal X-ray structure analysis of 3 revealed that this complex exists in the solid state as a centrosymmetric dimer containing two Ti-centered, face-sharing pseudooctahedra in the unique half of the dimer. Addition of 2 equiv of KO{sup i}Pr to a 2-propanol solution of 2 led to the formation of KO{sub 2}P(O{sup t}Bu){sub 2} (4) and Ti(O{sup i}Pr){sub 4} in high yield. Cooling a 2-propanol solution of 4 to {minus}80 C led to crystallization of the solvated tetramer [4 {center_dot} HO{sup i}Pr{sub 3}]{sub 4} (mp = {minus}30 C). A single-crystal X-ray structure analysis revealed that this tetramer possesses a cubelike K{sub 4}O{sub 4} core with 4-fold improper rotation symmetry. Multinuclear NMR studies of 1--3 show that the structures of these complexes are dynamic in solution. Crystals of 4 are tetragonal.
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 642373
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 8 Vol. 37; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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