TITLE

Formation of the chelate bonds in the cluster O-2(CO2)n, CO-3(CO2)n, and NO-2(CO2)n

AUTHOR(S)
Hiraoka, Kenzo; Yamabe, Shinichi
PUB. DATE
July 1992
SOURCE
Journal of Chemical Physics;7/1/1992, Vol. 97 Issue 1, p643
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
The equilibria of gas-phase clustering reactions of O-2, CO-3, and NO-2 with CO2 were studied with a pulsed electron beam high-pressure mass spectrometer. Thermochemical stabilities of the clusters O-2(CO2)n, CO-3(CO2)n, and NO-2(CO2)n with n=1–8 were determined. For O-2(CO2)n, irregular decreases in the values of -ΔH0n-1,n were observed between n=1 and 2, and n=3 and 4. These gaps indicate that the bond with covalent character is formed through the charge transfer (CT) O-2→CO2 and the CT complex of O2COO- accommodates two CO2 molecules preferably [i.e., O2COO-(CO2)2]. The -ΔH0n-1,n values of both CO-3(CO2)n and NO-2(CO2)n clusters show an irregular decrease between n=4 and 5. This suggests the formation of shells, OCO-2(CO2)4 and NO-2(CO2)4. Ab initio optimized geometries of these clusters are found to be composed of bridge (i.e., chelate) intermolecular bonds.
ACCESSION #
7616283

 

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