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Kinetic deuterium isotope effects in the protonations of ((/mu/-H)M/sub 3/(CO)/sub 11/)/sup /minus// (M = Fe, Ru, Os)

Journal Article · · Organometallics; (United States)
DOI:https://doi.org/10.1021/om00098a008· OSTI ID:5927540
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The rates of low-temperature (/minus/90 to /minus/40/degree/C) protonation of the anions ((/mu/-H)M/sub 3/(CO)/sub 11/)/sup /minus// (M = Fe, Ru, Os) have been investigated with XSO/sub 3/F (X = H or D) in CD/sub 2/Cl/sub 2/ by using /sup 1/H and /sup 13/C NMR techniques. No deuterium kinetic isotope effect is observed on the rate of protonation to give the initially formed oxygen-protonated species (/mu/-H)(COX)M/sub 3/(CO)/sub 10/ (M = Fe, Ru; X = H or D). However, in the case of ruthenium the rate of transformation of this species to the dihydrido species (/mu/-X)XRu/sub 3/(CO)/sub 11/ (X = H or D) shows a very large isotope effect (k/sub H//k/sub D/ = 47 at /minus/40/degree/C). In the case of osmium, the previously unobserved oxygen-deuteriated species (/mu/-H)(COD)Os/sub 3/(CO)/sub 10/ is seen at /minus/80/degree/C with DSO/sub 3/F. Under these conditions, protonation with HSO/sub 3/F yields only (/mu/-H)(H)Os/sub 3/(CO)/sub 11/. These large isotope effects on ligand to metal hydrogen transfer are discussed in connection with previously observed large isotope effects in cluster protonations.
Research Organization:
California State Univ., Northridge (USA)
OSTI ID:
5927540
Journal Information:
Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 7:8; ISSN ORGND
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
ANIONS
CARBON 13
CARBON ISOTOPES
CARBONYLS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DEUTERIUM
DEUTERIUM COMPOUNDS
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HYDROGEN 1
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
IONS
IRON COMPOUNDS
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGANDS
LIGHT NUCLEI
LOW TEMPERATURE
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ODD-ODD NUCLEI
OSMIUM COMPOUNDS
REACTION KINETICS
REFRACTORY METAL COMPOUNDS
RESONANCE
RUTHENIUM COMPOUNDS
STABLE ISOTOPES
TRANSITION ELEMENT COMPOUNDS