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

Journal Article · Wed Dec 19 04:00:00 EST 1990 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00182a016· OSTI ID:5730903

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

---

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

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.

• DOE Contract Number: FG02-86ER45231
• OSTI ID: 5730903
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 112:26; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

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