TOPOTACTIC ORGANOMETALLIC CHEMISTRY - INTRAZEOLITE CPCO(CO)2-M56Y, WHERE M=H, LI, NA, K, RB, AND CS

Date

1991-05-01

Author

LI, XP
OZIN, GA
Özkar, Saim

Metadata

Show full item record

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Item Usage Stats

197
views

0
downloads

The vibrational and electronic spectroscopy of precursor CpCo(CO)2-M56Y, where M = H, Li, Na, K, Rb, and Cs and Y refers to zeolite Y, is compared with that known for CpCo(CO)2 in the gas, solution, and matrix phases. In this way considerable insight is obtained concerning the subtle interplay of supercage topology, framework oxygen charge density, and extraframework cation local field effects on the geometric and electronic properties, as well as the type(s) of anchoring site(s) (cation versus oxygen framework) found for the guest molecules in the zeolite Y host lattice. These spectroscopic probes also permit one to evaluate the role of these zeolite support effects on the reactivity of anchored CpCo((CO)-C-12)2-M56Y toward (CO)-C-13 isotope exchange, phosphine substitution, and vacuum thermal decarbonylation as compared to the situation found with other supports and in other phases. Information pertinent to the identity and location of precursors and products and their anchoring site architecture (Cp ring versus carbonyl ligand versus cobalt interactions with the zeolite) emerges from the results of these experiments. Molecular graphics investigations allow one to propose topological models that account for the occurrence and nature of two distinct cation-based anchoring sites for precursor CpCo(CO)2-M56Y (ZOM...CpCo(CO)2 denoted site 1 and ZOM...(OC)2CoCp denoted site 2) as well as its in situ vacuum thermal decarbonylation product Cp2Co2(mu-2-CO)2-M56Y (symmetrical ZOM...CpCo(CO)2CoCp...MOZ denoted class I and symmetrical ZOM...(OC)Cp2Co2(CO)...MOZ denoted class II) over the entire alkali-metal cation series.

Subject Keywords

Physical and Theoretical Chemistry, General Engineering

URI

https://hdl.handle.net/11511/69907

Journal

JOURNAL OF PHYSICAL CHEMISTRY

DOI

https://doi.org/10.1021/j100164a055

Collections

Department of Chemistry, Article

Suggestions

OpenMETU
Core

Thermodynamic Parameters of Cholesteric/Smectic A Transition in Cholesteric Myristate and Its Binary Mixture CM/PCPB Yurtseven, Hasan Hamit (Pleiades Publishing Ltd, 2018-06-01) Thermodynamic properties of the cholesteryl myristate (CM) and its binary mixture CM/PCPB (p-pentylphenyl-2-chloro-4(p-pentylbenzoyl)-benzoate) are studied at the concentrations of x (PCPB) = 0.052 and 0.219 as a function of temperature near the cholosteric/smectic A transition. By analyzing the observed molar volume from the literature, the temperature dependences of the thermal expansion, isothermal compressibility and the difference in the specific heat are calculated and, the Pippard relations are estab...
INTRAZEOLITE TOPOTAXY - NA-23 DOUBLE-ROTATION NMR-STUDY OF TRANSITION-METAL HEXACARBONYLS AND OXIDES ENCAPSULATED IN SODIUM ZEOLITE-Y JELINEK, R; Özkar, Saim; OZIN, GA (American Chemical Society (ACS), 1992-07-01) Na-23 double-rotation NMR (DOR) provides details on site specific adsorption and anchoring interactions in intrazeolite hexacarbonylmetal(0) complexes, M{M(CO)6}-Na56Y, where M = Mo and W, and their molecular photooxidation products, n{MO3-x}-Na56Y, over the full composition range 0 < m less-than-or-equal-to 16, 0 < n less-than-or-equal-to 32 and 0 less-than-or-equal-to x less-than-or-equal-to 1. The shifts, intensities, and line shapes of the Na-23 DOR resonances carry information on the environments of th...
INTRAZEOLITE SEMICONDUCTORS - NA-23 MAS NMR, TL+ LUMINESCENCE QUENCHING, AND FAR-IR STUDIES OF ACID-BASE PRECURSOR CHEMISTRY IN ZEOLITE-Y MCMURRAY, L; HOLMES, AJ; KUPERMAN, A; OZIN, GA; Özkar, Saim (American Chemical Society (ACS), 1991-11-01) Proton-loaded zeolites, prepared from fully dehydrated zeolites and gaseous, anhydrous Bronsted acids, represent an important step in the synthesis of intrazeolite semiconductor quantum supralattices. Adsorption-induced Na-23 MAS NMR chemical shifts, far-IR Na+ and Tl+ translatory mode frequency shifts, and Tl+ luminescence quenching effects were chosen as probes of cation-anion interaction in these materials. Samples of zeolite Y with various loadings of Tl+ were prepared via aqueous ion-exchange techniq...
Dielectric Properties of Ethanol and Gasoline Mixtures by Terahertz Spectroscopy and an Effective Method for Determination of Ethanol Content of Gasoline ARIK, Enis; Altan, Hakan; Esentürk, Okan (American Chemical Society (ACS), 2014-05-01) Investigation of frequency dependent permittivity of mixture solutions provides information on the role of intermolecular interactions on relaxation processes of solvent and solute molecules. In this study the dielectric properties of ethanol/gasoline mixtures in the terahertz spectral region are investigated. Frequency dependent absorption coefficients, refractive indices, and complex permittivities of pure ethanol and gasoline, and their mixtures at varying ethanol volume percentages (v/v %) are reported....
Excitation Localization/Delocalization Isomerism in a Strongly Coupled Covalent Dimer of 1,3-Diphenylisobenzofuran Schrauben, Joel N.; Akdağ, Akın; Wen, Jin; Havlas, Zdenek; Ryerson, Joseph L.; Smith, Millie B.; Michl, Josef; Johnson, Justin C. (American Chemical Society (ACS), 2016-05-26) Two isomers of both the lowest excited singlet (S-1) and triplet (T-1) states of the directly para, para'-connected covalent dimer of the singlet-fission chromophore 1,3-diphenylisobenzofuran have been observed. In one isomer, excitation is delocalized over both halves of the dimer, and in the other, it is localized on one or the other half. For a covalent dimer in solution, such "excitation isomerism" is extremely rare. The vibrationally relaxed isomers do not interconvert, and their photophysical properti...

Citation Formats

X. LI, G. OZIN, and S. Özkar, “TOPOTACTIC ORGANOMETALLIC CHEMISTRY - INTRAZEOLITE CPCO(CO)2-M56Y, WHERE M=H, LI, NA, K, RB, AND CS,” JOURNAL OF PHYSICAL CHEMISTRY, pp. 4463–4476, 1991, Accessed: 00, 2021. [Online]. Available: https://hdl.handle.net/11511/69907.