Alkali metal-templated assembly of cyanometalate ``boxes'' (NEt{sub 4}){sub 3}{l{underscore}brace}M[Cp*Rh(CN){sub 3}]{sub 4}[Mo(CO){sub 3}]{sub 4}{r{underscore}brace} (M = K, Cs). Selective binding of Cs{sup +}
The box-like cages {l{underscore}brace}M[Cp*Rh(CN){sub 3}]{sub 4}[Mo(CO){sub 3}]{sub 4}{r{underscore}brace}{sup 3{minus}} form as the sole metal-containing products of the reaction of [Cp*Rh(CN){sub 3}]{sup {minus}} and ({eta}{sup 6}-C{sub 6}H{sub 3}Me{sub 3})Mo(CO){sub 3} in the presence of K{sup +} and Cs{sup +}. Well-defined species could not be identified in solutions of Cp*Rh(CN){sub 3}{sup {minus}} ({eta}{sup 6}-C{sub 6}H{sub 3}Me{sub 3})Mo(CO){sub 3} in the absence of alkali metal cations. The new cages were isolated as their Et{sub 4}N{sup +} salts, M = K{sup +} (1), Cs{sup +} (2). Crystallographic characterization of 1 and 2 reveals box-like M{sub 8}({micro}-CN){sub 12} cages containing alkali metal cations. The cages feature 12 external CO and 4 external C{sub 5}Me{sub 5} ligands. In 1, the K{sup +} is disordered over two off-center positions, whereas in the case of 2, the Cs{sup +} is centered in the cage with a formal coordination number of 24. Otherwise, the structures of the two compounds are virtually indistinguishable. The persistence of the solid-state structures in solution was established through {sup 13}C NMR spectroscopy and electrospray mass spectrometric measurements. {sup 133}Cs NMR spectroscopy, which readily distinguishes free from included Cs{sup +}, shows that the boxes preferentially bind Cs{sup +} relative to K{sup +}.
- Research Organization:
- Univ. of Illinois, Urbana, IL (US)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- FG02-90ER14146; FG02-91ER45439
- OSTI ID:
- 20013112
- Journal Information:
- Journal of the American Chemical Society, Vol. 121, Issue 12; Other Information: PBD: 31 Mar 1999; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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