FTIR matrix isolation studies of the reactions of atomic and diatomic nickel with acetylene in solid argon. The photosynthesis of nickel vinylidene
The reactions between atomic nickel and acetylene have been investigated in argon matrices at 12 K with Fourier-transform infrared spectroscopy. At very low concentrations of nickel and acetylene the nickel atom forms a ..pi.. complex with the triple bond of acetylene. This ..pi.. complex photorearranges upon visible photolysis with lambda greater than or equal to 400 nm to give nickel vinylidene, NiCCH/sub 2/. Photolysis with ultraviolet light causes the reversal of this reaction. Isotopic studies with C/sub 2/D/sub 2/, C/sub 2/HD, /sup 13/C/sub 2/H/sub 2/, and /sup 12/C/sup 13/CH/sub 2/ support these findings. The FTIR spectrum of a dinickel-acetylene ..pi.. complex obtained at higher nickel concentrations has also been identified. The bond order of acetylene has been reduced to two in both Ni(C/sub 2/H/sub 2/) and Ni/sub 2/(C/sub 2/H/sub 2/), as evidenced from the big shift in the carbon-carbon stretching frequency. No photochemistry was observed in the case of the dinickel reaction.
- Research Organization:
- Rice Univ., Houston, TX
- OSTI ID:
- 6538226
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 109:8
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACETYLENE
CHEMICAL REACTIONS
PHOTOLYSIS
DEUTERIUM COMPOUNDS
ISOTOPE EFFECTS
NICKEL
ARGON
EXPERIMENTAL DATA
FOURIER TRANSFORM SPECTROMETERS
INFRARED SPECTRA
MATRIX ISOLATION
ULTRALOW TEMPERATURE
ALKYNES
DATA
DECOMPOSITION
ELEMENTS
FLUIDS
GASES
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
MEASURING INSTRUMENTS
METALS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
RARE GASES
SPECTRA
SPECTROMETERS
TRANSITION ELEMENTS
400500* - Photochemistry