/sup 1/H, /sup 47/Ti, and /sup 49/Ti ENDOR study on frozen solutions of ((eta/sup 5/-C/sub 5/H/sub 5/)Ti(eta/sup 8/-C/sub 8/H/sub 8/)) and ((eta/sup 5/-CH/sub 3/ x C/sub 5/H/sub 4/)Ti(eta/sup 8/-C/sub 8/H/sub 8/))
The paramagnetic mixed sandwich compounds CpTicot and Me-CpTicot (Cp = eta/sup 5/-C/sub 5/H/sub 5/, Me-Cp = eta/sup 5/-CH/sub 3/-C/sub 5/H/sub 4/, cot = eta/sup 8/-C/sub 8/H/sub 8/) were studied by ENDOR. It is shown for the first time that signals due to /sup 47/Ti and /sup 49/Ti nuclei in natural abundance can be resolved in dilute frozen solutions. These data yielded a measure of the quadrupole interaction from which a negative field gradient at the Ti nucleus could be deduced, indicating that the d/sub x/sup 2/-y/sup 2// and d/sub xy/ metal orbitals are significantly occupied. Proton ENDOR below 60 K allowed us to measure the principal values of the hyperfine tensor and to deduce proton coordinates from a simple point dipole model. The onset of fast ring reorientation above 60 K is clearly manifested by a gradual transformation of the low-temperature, powderlike ENDOR spectrum into a single crystallike spectrum. The effect of methyl substitution on Cp rings demonstrates that the ring reorientation is only governed by intermolecular interactions.
- OSTI ID:
- 6181949
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:15; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
COMPLEXES
DATA
DOUBLE RESONANCE METHODS
ELECTRIC FIELDS
ELECTRONIC STRUCTURE
ENDOR
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HYDROGEN 1
HYDROGEN ISOTOPES
INFORMATION
INTERMEDIATE MASS NUCLEI
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
QUADRUPOLE MOMENTS
RESONANCE
STABLE ISOTOPES
TITANIUM 47
TITANIUM 49
TITANIUM COMPLEXES
TITANIUM ISOTOPES
TRANSITION ELEMENT COMPLEXES
VERY LOW TEMPERATURE