title: Polyoxoanion-Supported Organometallic Complexes: Carbonyls of Rhenium(I), Iridium(I), and Rhodium(I) That Are Soluble Analogs of Solid-Oxide-Supported M(CO)(n)()(+) and That Exhibit Novel M(CO)(n)()(+) Mobility.
abstract: The Dawson-type P(2)W(15)Nb(3)O(62)(9)(-) polyoxoanion-supported Re(CO)(3)(+) complex, [Re(CO)(3).P(2)W(15)Nb(3)O(62)](8)(-) (1), has been synthesized and characterized in two different counter-cation compositions. The [(n-C(4)H(9))(4)N](8)(8+) complex provides a highly soluble compound which exists as a single isomer in solution. The carbonyl stretching infrared frequencies suggest that the P(2)W(15)Nb(3)O(62)(9)(-) ligand serves as a strong electron donor to the Re(CO)(3)(+) fragment. The P(2)W(15)Nb(3)O(62)(9)(-) polyoxoanion-supported Ir(CO)(2)(+) complex [Ir(CO)(2).P(2)W(15)Nb(3)O(62)](8)(-) (2) has also been synthesized and characterized as its octakis(tetrabutylammonium), [(n-C(4)H(9))(4)N](8)(8+), salt. This compound was characterized by NMR and IR, results which demonstrate that 2 also exists as a single isomer in solution. The [Ir(CO)(2).P(2)W(15)Nb(3)O(62)](8)(-) complex is stable in the absence of water, but decomposes quickly in the presence of even 1 equiv of water. Attempted preparation of the analogous P(2)W(15)Nb(3)O(62)(9)(-) -supported Rh(CO)(2)(+) complex (3), while monitoring by (31)P NMR, revealed that this compound is unstable in solution at room temperature. In addition, we have discovered that added Na(+) can induce the formation of non-C(3)(v)() symmetry isomers of supported Re(CO)(3)(+) and Ir(CO)(2)(+) and, by inference, supported Ir(1,5-COD)(+). When Na(+) is removed from these systems by addition of Kryptofix[2.2.2], the non-C(3)(v)() isomers convert back to the single, C(3)(v)() isomer with heating, thereby providing a model system for the little studied mobility of M(CO)(n)()(+) cations across a soluble-oxide surface. When [Rh(CO)(2).P(2)W(15)Nb(3)O(62)](8)(-) is irradiated in the presence of hydrogen and cyclohexene a novel polyoxoanion-stabilized Rh(0)(n)() nanocluster is formed, results that bear a strong analogy to Yates' work studying atomically-dispersed Rh(CO)(2)(+) on solid Al(2)O(3).(10e) Yates and co-workers observe that Rh(CO)(+).Al(2)O(3) loses a CO upon photolysis, and that the resultant Rh(CO)(1)(+).Al(2)O(3) is reduced under H(2) to form Rh(0), which in turn yields Rh(0)(n)() clusters on Al(2)O(3)-a process that, intriguingly, is largely reversible if CO is readded. Also briefly discussed is other relevant literature of solid-oxide-supported Re(CO)(3)(+) and M(CO)(2)(+) (M = Ir, Rh), literature that makes apparent the potential significance of these complexes as EXAFS and other spectroscopic models of solid-oxide-supported M(CO)(n)()(+).
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523.
authors.forename: Toshi
authors.initials: T
authors.lastname: Nagata
authors.forename: Matthias
authors.initials: M
authors.lastname: Pohl
authors.forename: Heiko
authors.initials: H
authors.lastname: Weiner
authors.forename: Richard G.
authors.initials: RG
authors.lastname: Finke