Hydrogen-deuterium exchange of the anionic group 6B transition-metal hydrides. Convenient, in-situ-deuterium transfer reagents

Journal Article · Wed Aug 22 00:00:00 EDT 1984 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00329a019· OSTI ID:6320248

Gaus, P L; Kao, S C; Darensbourg, M Y; Arndt, L W

The facile exchange of hydrogen for detuerium in the anionic group 6B carbonyl hydrides HM(CO)/sub 4/L/sup -/(M = Cr, W; L = CO P(OMe)/sub 3/) has been studied in THF/sub 4/ (tetrahydrofuran) with CH/sub 3/OD, D/sub 2/O, and CH/sub 3/CO/sub 2/D. This has provided a synthesis of the deuterides, DM(CO)/sub 4/L/sup -/, as well as a convenient in situ source of deuteride reducing reagents for organic halides. A number of such reductions are described, using /sup 2/H NMR to demonstrate both selectivity and stereospecificity for certain systems. The carbonyl region of the infrared spectra of the hydrides is not affected by deuteration of the hydrides, suggesting that the M-H or M-D vibrational modes are not coupled significantly to CO vibrations in these hydrides. The mechanism of the H/D exchange and of a related H/sub 2/ elimination reaction is discussed.

• Research Organization: Texas A and M Univ., College Station
• OSTI ID: 6320248
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 106:17; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
400203* -- Isotope Exchange & Isotope Separation-- (-1987)
ACETIC ACID
ALCOHOLS
CARBONYLS
CARBOXYLIC ACIDS
CHROMIUM COMPOUNDS
CHROMIUM HYDRIDES
COMPARATIVE EVALUATIONS
DATA
DEUTERIUM
DEUTERIUM COMPOUNDS
EXPERIMENTAL DATA
FURANS
HEAVY WATER
HETEROCYCLIC COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
INFORMATION
INFRARED SPECTRA
ISOTOPE EFFECTS
ISOTOPES
ISOTOPIC EXCHANGE
LIGHT NUCLEI
METHANOL
MONOCARBOXYLIC ACIDS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
OXYGEN COMPOUNDS
REFRACTORY METAL COMPOUNDS
SPECTRA
STABLE ISOTOPES
TETRAHYDROFURAN
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN COMPOUNDS
TUNGSTEN HYDRIDES
WATER