Influence of the alkoxide moiety on heterometallic compound formation: Structure and dynamics of KZr{sub 2}(O{sup t}Bu){sub 9} and K{sub 2}Zr{sub 2}(O{sup 5}Bu){sub 10}
- Indiana Univ., Bloomington, IN (United States)
KZr{sub 2}(O{sup t}Bu){sub 9} was prepared by reaction of KO{sup t}Bu with Zr(O{sup t}Bu){sub 4} in a 1:2 molar ratio. Attempted sublimation results in dissociation of Zr(O{sup t}Bu){sub 4}, affording [KZr(O{sup t}Bu){sub 5}]{sub n}, which can also be synthesized using equimolar KO{sup t}Bu and Zr(O{sup t}Bu){sub 4}. Single-crystal X-ray diffraction revealed that n=2: K{sub 2}Zr{sub 2}(O{sup t}Bu){sub 10} crystallizes from pentane at -20 {degrees}C in the monoclinic space group P2{sub 1}/c, with the unit cell dimensions a = 10.532(1) {Angstrom}, b = 18.057(3) {Angstrom}, c = 27.618(5) {Angstrom}, {beta} = 95.54(1){degrees}, and Z = 4. The dimer is composed of two five-coordinate Zr centers, each having trigonal bipyramidal geometry; the axes of the trigonal bipyramide are orthogonal, and the Zr(O{sup t}Bu){sub 5}{sup {minus}} units encapsulate both potassiums. Due to fluxionality, this species appears as a singlet in {sup 1}H NMR in d{sub 8}-toluene even at -75 {degrees}C. Interconversions between and possible dissociative reactions of KZr{sub 2}(O{sup t}Bu){sub 9} and [KZr(O{sup t}Bu){sub 5}]{sub 2} are also tested experimentally.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 416518
- Journal Information:
- Inorganic Chemistry, Vol. 33, Issue 26; Other Information: PBD: 21 Dec 1994
- Country of Publication:
- United States
- Language:
- English
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