Alcohol adducts of alkoxides: Intramolecular hydrogen bonding as a general structural feature

Journal Article · Wed Aug 22 04:00:00 EDT 1990 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00342a014· OSTI ID:6332068

Vaartstra, B A; Huffman, J C; Caulton, K G ^[1]; Gradeff, P S; Yunlu, K ^[2]; Hubert-Pfalzgraf, L G; Parraud, S ^[3]; Daran, J C ^[4]

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1. Indiana Univ., Bloomington (USA)
2. Rhone-Poulenc, Inc., New Brunswick, NJ (USA)
3. Universite de Nice (France)
4. Universite Pierre et Marie Curie, Paris (France)

Characterization of Zr{sub 2}(O{sup i}Pr){sub 8}({sup i}PrOH){sub 2} by {sup 1}H and {sup 13}C NMR spectroscopy, ir spectroscopy, and single-crystal x-ray diffraction ({minus}100{degree}C) is reported. The unit cell contains four half-dimers in the asymmetric unit, all of which differ only in the rotational conformation about Zr-O and O-C bonds. In each dimer, the edge-shared bioctahedron has two {mu}-O{sup i}Pr groups. On opposite sides of this Zr{sub 2}({mu}-OR){sub 2} plane, each dimer forms two hydrogen bonds, one each between a coordinated alcohol and a terminal alkoxide. The NMR spectra at 25{degree}C are so simple as to be structurally uninformative, a result of rapid fluxionality which includes, as one component, proton migration among all O{sup i}Pr units. At {minus}80{degree}C in toluene, the NMR spectra are now too complex to be accounted for by a single edge-shared bioctahedral structure. The hafnium analogue is isomorphous with the zirconium compound. Although Ce{sub 2}(O{sup i}Pr){sub 8}({sup i}PrOH){sub 2} is not isomorphous, it exhibits an analogous hydrogen-bonded structure in which the O{hor ellipsis}O distance is as short as it is in the Zr analogue, in spite of a metal-metal separation which is longer by 0.28 {angstrom}. The generality of hydrogen bonding between M-OR and M-O(H)R groups when they are aligned parallel in a metal cluster is reviewed. 44 refs., 2 figs., 4 tabs.

• OSTI ID: 6332068
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 29:17; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ADDUCTS
ALCOHOLS
ALKOXIDES
BARYONS
CARBON 13
CARBON ISOTOPES
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
CRYSTALS
DATA
DIFFRACTION
ELEMENTARY PARTICLES
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
FERMIONS
HADRONS
HYDROXY COMPOUNDS
INFORMATION
INFRARED SPECTRA
ISOTOPES
LIGHT NUCLEI
MONOCRYSTALS
NMR SPECTRA
NUCLEI
NUCLEONS
NUMERICAL DATA
ORGANIC COMPOUNDS
PRASEODYMIUM COMPLEXES
PROTONS
RARE EARTH COMPLEXES
SCATTERING
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION
ZIRCONIUM COMPLEXES