Intrazeolite metal carbonyl topotaxy. A comprehensive structural and spectroscopic study of intrazeolite group VI metal hexacarbonyls and subcarbonyls

Oezkar, S; Ozin, G A; Moller, K; Bein, T

doi:10.1021/ja00182a016

Title: Intrazeolite metal carbonyl topotaxy. A comprehensive structural and spectroscopic study of intrazeolite group VI metal hexacarbonyls and subcarbonyls

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Abstract

This paper focuses attention on the intrazeolite anchoring, thermal decarbonylation, ligand exchange, and addition chemistry of M(CO){sub 6}-M{prime}{sub 56}Y, where M = Cr, Mo, W; M{prime} = H, Li, Na, K, Rb, Cs. The key points to emerge from this study include the following. (1) M(CO){sub 6}-M{prime}{sub 56}Y samples have the hexacarbonylmetal(0) molecule associated with two {alpha}-cage extraframework cations (or Broensted protons), via the oxygen end of two trans bonded carbonyls with a saturation loading of 2M(CO){sub 6}/{alpha}-cage. (2) M(CO){sub 6}-M{prime}{sub 56}Y samples have the hexacarbonylmetal(0) guest confined to the internal surface of the zeolite with a homogeneous distribution throughout the zeolite crystals. (3) A Mo and Rb EXAFS structure analysis of 8{l brace}Mo(CO){sub 6}{r brace}-Rb{sub 56}Y shows that the {alpha}-cage encapsulated Mo(CO){sub 6} guest maintains its structural integrity, with some evidence for anchoring via extraframework Rb+ cations. (4) A rapid {sup 13}CO intrazeolite ligand exchange occurs for M({sup 12}CO){sub 6}-M{prime}{sub 56}Y to yield M({sup 12}CO){sub m}({sup 13}CO){sub 6-m}-M{prime}{sub 56}Y, the extent of which depends on the {sup 13}CO intrazeolite ligand exchange occurs for M({sup 12}CO){sub 6}-M{prime}{sub 56}Y to yield M({sup 12}CO){sub m}({sup 13}CO){sub 6-m}-M{prime}{sub 56}Y, the extent of which depends on the {sup 13}CO loading. (5) M(CO){sub 3}-M{prime}{sub 56}Ymore »« less

Authors:

Oezkar, S; Ozin, G A ^[1]; Moller, K; Bein, T ^[2]

Univ. of Toronto, Ontario (Canada)
Univ. of New Mexico, Albuquerque (United States)

Publication Date:: Wed Dec 19 00:00:00 EST 1990

OSTI Identifier:: 5730903

DOE Contract Number:: FG02-86ER45231

Resource Type:: Journal Article

Journal Name:: Journal of the American Chemical Society; (United States)

Additional Journal Information:: Journal Volume: 112:26; Journal ID: ISSN 0002-7863

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHROMIUM COMPLEXES; CHEMICAL REACTIONS; MOLYBDENUM COMPLEXES; ZEOLITES; ABSORPTION SPECTROSCOPY; ANNEALING; CARBON 13; CARBONYLS; CESIUM COMPOUNDS; CHEMICAL PREPARATION; COMPUTER CALCULATIONS; CRYSTALLOGRAPHY; DECOMPOSITION; ENERGY LEVELS; INFRARED SPECTRA; JAHN-TELLER EFFECT; LIGANDS; LITHIUM COMPOUNDS; MATHEMATICAL MODELS; MOLECULAR STRUCTURE; OPTICAL REFLECTION; PHOSPHINES; POTASSIUM COMPOUNDS; RUBIDIUM COMPOUNDS; RUBIDIUM IONS; SODIUM COMPOUNDS; SORPTION; STOICHIOMETRY; THERMOCHEMICAL PROCESSES; TUNGSTEN COMPLEXES; VIBRATIONAL STATES; X-RAY DIFFRACTION; X-RAY SPECTROSCOPY; ALKALI METAL COMPOUNDS; CARBON ISOTOPES; CHARGED PARTICLES; COHERENT SCATTERING; COMPLEXES; DIFFRACTION; EVEN-ODD NUCLEI; EXCITED STATES; HEAT TREATMENTS; INORGANIC ION EXCHANGERS; ION EXCHANGE MATERIALS; IONS; ISOTOPES; LIGHT NUCLEI; MATERIALS; MINERALS; NUCLEI; PHOSPHORUS COMPOUNDS; REFLECTION; SCATTERING; SILICATE MINERALS; SPECTRA; SPECTROSCOPY; STABLE ISOTOPES; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties

Citation Formats


                    Oezkar, S, Ozin, G A, Moller, K, and Bein, T. Intrazeolite metal carbonyl topotaxy. A comprehensive structural and spectroscopic study of intrazeolite group VI metal hexacarbonyls and subcarbonyls.  United States: N. p., 1990. 
        Web.  doi:10.1021/ja00182a016.

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                    Oezkar, S, Ozin, G A, Moller, K, & Bein, T. Intrazeolite metal carbonyl topotaxy. A comprehensive structural and spectroscopic study of intrazeolite group VI metal hexacarbonyls and subcarbonyls.  United States.  https://doi.org/10.1021/ja00182a016

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                    Oezkar, S, Ozin, G A, Moller, K, and Bein, T. 1990.  
        "Intrazeolite metal carbonyl topotaxy. A comprehensive structural and spectroscopic study of intrazeolite group VI metal hexacarbonyls and subcarbonyls".  United States.  https://doi.org/10.1021/ja00182a016.

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@article{osti_5730903,

  title        = {Intrazeolite metal carbonyl topotaxy. A comprehensive structural and spectroscopic study of intrazeolite group VI metal hexacarbonyls and subcarbonyls},

  author       = {Oezkar, S and Ozin, G A and Moller, K and Bein, T},

  abstractNote = {This paper focuses attention on the intrazeolite anchoring, thermal decarbonylation, ligand exchange, and addition chemistry of M(CO){sub 6}-M{prime}{sub 56}Y, where M = Cr, Mo, W; M{prime} = H, Li, Na, K, Rb, Cs. The key points to emerge from this study include the following. (1) M(CO){sub 6}-M{prime}{sub 56}Y samples have the hexacarbonylmetal(0) molecule associated with two {alpha}-cage extraframework cations (or Broensted protons), via the oxygen end of two trans bonded carbonyls with a saturation loading of 2M(CO){sub 6}/{alpha}-cage. (2) M(CO){sub 6}-M{prime}{sub 56}Y samples have the hexacarbonylmetal(0) guest confined to the internal surface of the zeolite with a homogeneous distribution throughout the zeolite crystals. (3) A Mo and Rb EXAFS structure analysis of 8{l brace}Mo(CO){sub 6}{r brace}-Rb{sub 56}Y shows that the {alpha}-cage encapsulated Mo(CO){sub 6} guest maintains its structural integrity, with some evidence for anchoring via extraframework Rb+ cations. (4) A rapid {sup 13}CO intrazeolite ligand exchange occurs for M({sup 12}CO){sub 6}-M{prime}{sub 56}Y to yield M({sup 12}CO){sub m}({sup 13}CO){sub 6-m}-M{prime}{sub 56}Y, the extent of which depends on the {sup 13}CO intrazeolite ligand exchange occurs for M({sup 12}CO){sub 6}-M{prime}{sub 56}Y to yield M({sup 12}CO){sub m}({sup 13}CO){sub 6-m}-M{prime}{sub 56}Y, the extent of which depends on the {sup 13}CO loading. (5) M(CO){sub 3}-M{prime}{sub 56}Y can be cleanly generated via the mild vacuum thermal decarbonylation of M(CO){sub 6}-M{prime}{sub 56}Y, the tricarbonyl stoichiometry of which is unequivocally established from its observed ad calculated diagnostic M({sup 12}CO){sub n}({sup 13}CO){sub 3-n}-M{prime}{sub 56}Y vibrational isotope pattern and from EXAFS structural data.},

  doi          = {10.1021/ja00182a016},

  url          = {https://www.osti.gov/biblio/5730903},
  journal      = {Journal of the American Chemical Society; (United States)},

  issn         = {0002-7863},

  number       = ,

  volume       = 112:26,

  place        = {United States},

  year         = {Wed Dec 19 00:00:00 EST 1990},

  month        = {Wed Dec 19 00:00:00 EST 1990}

}

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