A new look at an old reaction: The potential energy surface for the thermal carbonylation of Mn(CO)5CH3. The role of two energetically competitive intermediates on the reaction surface, and comments on the photodecarbonylation of Mn(CO)5(COCH3)

Journal of the American Chemical Society

Volumn 122, Issue 9, 2000, Pages 2078-2086

  Derecskei Kovacs, Agnes ^a,b   Marynick, Dennis S ^a  

^a UNIVERSITY OF TEXAS AT ARLINGTON   (United States)

^b TEXAS A AND M UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBONYL DERIVATIVE; MANGANESE DERIVATIVE;

ARTICLE; CHEMICAL REACTION; CONFORMATION; CONTROLLED STUDY; DIELECTRIC CONSTANT; ENERGY TRANSFER; KINETICS; MATHEMATICAL COMPUTING; REACTION ANALYSIS;

EID: 0034620771     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja993441v     Document Type: Article

References (50)

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44. It should be noted that, if the DFT energetics are correct and ts1 is only 0.1 kcal/mol less stable than e, then applying the steady-state approximation to e would probably not be valid at room temperature. In this case, the reaction is best thought of as being concerted and the calculated activation energy is 19.8 kcal/mol. However, as noted earlier, we think it is more likely that DFT is underestimating this energy difference and that e is a true intermediate.
45. It is also possible that the agostic form e is not involved in the migration step at all. We could envision a third channel, in which ts2 is the transition state between the reactant and the dihapto species, which is then attacked by CO. A detailed kinetic analysis of this third channel leads to conclusions essentially identical with those for channel 2.
46. It should be noted that if in fact the QCISD energetics more accurately reflect the relative energies of the stationary points, then the dihapto structure is completely inaccessible from the reactant side due to the very high energy of ts2 at this level. In fact, the B3LYP/lb energetics which we have chosen to use in our kinetic and thermodynamic analyses yield the lowest relative energy for ts2 and therefore represent a best-case scenario for the channel 2 mechanism.
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48. As alluded to earlier, Calderazzo and Cotton assumed that the solvent effects observed were mainly a function of the bulk dielectric constant stabilizing a polar transition state and not specific solvent participation. In fact, the calculated dipole moments of all of the transition states and intermediates are considerably higher than that of the reactant. From the B3P86/sb calculations, we find the following (in Debye): a (0.3), e (3.0), d (3.0), ts1 (2.4), ts2 (2.7) ts3 (2.1), ts4 (3.8), and ts5 (1.0).
49. It is thought that photodissociation of b occurs only for carbonyls cis to the acyl group (ref 19).
50. In fact, in their first paper (ref 18) Boese and Ford argued that the similarity of the CO frequencies in methylcyclohexane and THF implied that the dihapto form existed in both solvents. Only in their second paper did they use reactivity arguments to conclude that coordinating solvents explicitly solvated the intermediate.