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

Journal Article · Wed Aug 22 00:00:00 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), Vol. 29:17; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

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