Nuclear magnetic resonance kinetic study of the intramolecular rearrangement of 2-(5-cyanotetraazolato)pentaammine cobalt (III) perchlorate

Conference · Sun Jan 01 04:00:00 EST 1984

OSTI ID:6945883

Pitre, E M; Attalla, A

The activation energy, E/sub a/, for the intramolecular rearrangement of the secondary explosive transition metal coordination compound 2-(5-cyanotetraazolato)pentaammine cobalt (III) perchlorate (CP) to its amidine complex was determined by variable temperature nuclear magnetic resonance (NMR) spectroscopy. A 30 wt % concentration of CP dissolved in deuterated dimethylsulfoxide (DMSO-d/sub 6/) was heated at five different temperatures for sufficient time to effect its transformation to the amidine complex. A specific reaction rate constant, k, was determined at each temperature from the rate of rearrangement of CP(d(amidine)/dt). Temperatures ranged from 60/sup 0/ to 100/sup 0/C in 10/sup 0/ increments. Transformations above 100/sup 0/C were too rapid to collect accurate data and too slow below 60/sup 0/C, requiring long collection periods. The Arrhenius relationship ((k = Aexp(-E/sub a//RT)) was applied to a plot of log k versus reciprocal absolute temperature where the slope is -E/sub a//2.303R and the activation energy was obtained. The variable temperature NMR method, as well as the analytical techniques used to obtain the kinetic data, are presented, and the final results are discussed.

• Research Organization: Monsanto Research Corp., Miamisburg, OH (USA). Mound
• DOE Contract Number: AC04-76DP00053
• OSTI ID: 6945883
• Report Number(s): MLM-3153(OP); CONF-8404153-1; ON: DE84012397
• Country of Publication: United States
• Language: English

Related Subjects

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEFENSE
450100* -- Military Technology
Weaponry
& National Defense-- Chemical Explosions & Explosives
ACTIVATION ENERGY
CHEMICAL EXPLOSIVES
CHEMICAL REACTION KINETICS
CHLORINE COMPOUNDS
COBALT COMPLEXES
COMPLEXES
DEUTERIUM COMPOUNDS
DMSO
ENERGY
EXPLOSIVES
HALOGEN COMPOUNDS
HYDROGEN COMPOUNDS
KINETICS
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXYGEN COMPOUNDS
PERCHLORATES
REACTION KINETICS
RESONANCE
STABILITY
SULFOXIDES
TEMPERATURE DEPENDENCE
TRANSITION ELEMENT COMPLEXES