Kinetic deuterium isotope effects on ligand migrations in metal hydrides
Creators
- 1. California State Univ., Northridge (USA)
- 2. Universita di Torino (Italy)
Description
Variable-temperature (VT) 1H and 13C NMR studies of the complexes (μ-X)2Os3(CO)9(μ3-η2-(CH3CH2)2C2) (X = H or D) reveal that alkyne migration over the face of the cluster is directly linked to hydride migrations on the metal core as evidenced by a temperature-independent isotope effect (kHH/kDD = 1.7). In a related study of the VT 13C NMR of (μ-X)2M3(CO)9(μ3-S) (X = H or D; M = Ru, Os) the observation of a kHH/kDD = 1.6 for both the osmium and ruthenium complexes demonstrates that the first stage of carbonyl averaging is brought about by hydride migration and not axial-radial exchange of carbonyl groups, a process that occurs only at higher temperatures. The mechanistic implications of these results are discussed in the context of the reactivity of metal clusters and the dynamic properties of the metal-hydrogen bond
Additional details
Publishing Information
- Journal Title
- Organometallics
- Journal Volume
- 9
- Journal Issue
- 5
- Series
- Organometallics.
- Journal Page Range
- 1379-1382
- ISSN
- 0276-7333
- CODEN
- ORGND
INIS
- Country of Publication
- United States
- Country of Input or Organization
- United States
- INIS RN
- 22011473
- Subject category
- S37: INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY;
- Resource subtype / Literary indicator
- Numerical Data
- Descriptors DEI
- DATA PROCESSING; DEUTERIUM; EXPERIMENTAL DATA; ISOTOPE EFFECTS; LIGANDS; MEASURING INSTRUMENTS; MEASURING METHODS; OSMIUM COMPLEXES; POPULATION DYNAMICS; RUTHENIUM HYDRIDES
- Descriptors DEC
- COMPLEXES; DATA; HYDRIDES; HYDROGEN COMPOUNDS; HYDROGEN ISOTOPES; INFORMATION; ISOTOPES; LIGHT NUCLEI; NUCLEI; NUMERICAL DATA; ODD-ODD NUCLEI; RUTHENIUM COMPOUNDS; STABLE ISOTOPES; TRANSITION ELEMENT COMPLEXES; TRANSITION ELEMENT COMPOUNDS