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Titolo:
BU4N)(2)[(IR(1,5-COD))(6)W4O16]CENTER-DOT-2CH(3)CN - A HYBRID INORGANIC-ORGANOMETALLIC, FLEXIBLE CAVITY HOST, ACETONITRILE-GUEST COMPLEX COMPOSED OF A [W4O4](N-SUPPORTED (1,5-COD)IR+ ORGANOMETALLIC GROUPS() TETRATUNGSTATE CUBE AND 6 POLYOXOANION)
Autore:
HAYASHI Y; MULLER F; LIN Y; MILLER SM; ANDERSON OP; FINKE RG;
Indirizzi:
COLORADO STATE UNIV,DEPT CHEM FT COLLINS CO 80523 COLORADO STATE UNIV,DEPT CHEM FT COLLINS CO 80523
Titolo Testata:
Journal of the American Chemical Society
fascicolo: 47, volume: 119, anno: 1997,
pagine: 11401 - 11407
SICI:
0002-7863(1997)119:47<11401:B-AHI>2.0.ZU;2-1
Fonte:
ISI
Lingua:
ENG
Soggetto:
MANGANESE ALKOXIDE CUBES; CATALYST PRECURSORS; MOLECULAR-STRUCTURE; WATER OXIDATION; PHOTOSYSTEM-II; CUBANE; CLUSTER; CHEMISTRY; CRYSTAL; MECHANISM;
Tipo documento:
Article
Natura:
Periodico
Citazioni:
60
Recensione:
Indirizzi per estratti:
Citazione:
Y. Hayashi et al., "BU4N)(2)[(IR(1,5-COD))(6)W4O16]CENTER-DOT-2CH(3)CN - A HYBRID INORGANIC-ORGANOMETALLIC, FLEXIBLE CAVITY HOST, ACETONITRILE-GUEST COMPLEX COMPOSED OF A [W4O4](N-SUPPORTED (1,5-COD)IR+ ORGANOMETALLIC GROUPS() TETRATUNGSTATE CUBE AND 6 POLYOXOANION)", Journal of the American Chemical Society, 119(47), 1997, pp. 11401-11407

Abstract

The tetratungstate polyoxoanion-supported organometallic compound 2CH(3)CN subset of(n-Bu4N)(2)[(lr( 1,5-COD))(6)W4O16]. 2CH(3)CN (2CH(3)CNsubset of 1 . 2CH(3)CN) is reported, a complex which exhibits an unusual ''methyl-first'' CH3CN inclusion (''subset of'') chemistry. The synthesis of 2CH(3)CN subset of 1 . 2CH(3)CN was accomplished by the reaction of 3 equiv of [Ir(1,S-COD)Cl](2) with 4 equiv of (n-Bu4N)(2)WO4;an X-ray diffraction single-crystal structure shows that the four tungsten atoms in of 2CH(3)CN subset of 1 . 2CH(3)CN are located in tetrahedral positions and combine with four bridging oxygens to yield a tungsten-oxygen cubane structure. The cubane core tungsten atoms are capped by six surrounding Clr(1,S-COD)](+) groups in an octahedral arrangement relative to the cube, with each [Ir(1,S-COD)](+) group coordinated by two terminal oxygen atoms from the tetratungstate unit. Two sets of flexible acetonitrile-binding cavities, formed between each three of the six [Ir(1,S-COD)](+) groups, form a roughly tetrahedral array surrounding the cube. This host-guest complex binds acetonitrile methyl-first, that is, with the methyl group rather than the nitrile group oriented toward a cubane core oxygen atom. The C-Me... O nonbonded distances fall in the range 3.10-4.46 Angstrom for C-Me...-(mu(2)-O) and 3.08-4.02 Angstrom for C-Me...(mu(3)-O) Acetonitrile-free 1 was also prepared, and its possible acetonitrile and toluene complexation in benzene and methylene chloride solution was studied by NMR. No binding between acetonitrile or toluene and I in solution is observed, even when using greater than 300 mol equiv of guest relative to 1. Therefore, thehost-guest interaction between 1 and acetonitrile appears to be weak (K-eq ( 10 M-1), possibly being limited to the solid state.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 05/12/20 alle ore 10:35:17