DFT Reactivity Descriptors and Catalysis - Vrije Universiteit Brussel

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Activation energies <strong>and</strong> rate constants catalytic activity AlCl 3 > BF 3 > Al(OH) 3 > L1 • AlCl 3 most efficient catalyst in agreement with experimental studies on relative efficiencies of metalhalides (Russell, Olah) • more appropriate in H- exchange reactions (not shown) • influence of surrounding atoms? Crystal calculations Interpretation? Pag. 30-9-2008 32
Cyclic TS characterized by several interactions of the electrophilic/nucleophilic type N Calculated TS with CH 3 F/BF 3 CH 3+ attacking benzene E C m C b E H 2 H + leaving benzene X - leaving CH 3 X X 1 N M E X 2 N C m H 3Cb X 1 H 2 X 3 X M 2 tsM_BF 3 X 3 X 4 orbital interactions (eg vacant orbital(s) of Lewis acids) > electrostatics softness at work? HSAB at local level A ..... B s A + as close possible to s B - + - Multicenter event: looking for smallest value of ∑( s -s ) 2 A,i B,i Cfr. regioselectivity of Diels Alder reactions showing cyclic TS. S. Damoun, G. V<strong>and</strong>e Woude, F. Mendez, P. Geerlings, J.Phys.Chem.A, 101, 886 (1997) i Pag. 30-9-2008 33
Page 1 and 2: DFT Reactivity Descriptors and Cata
Page 3 and 4: Outline 1. Robert Schoonheydt and t
Page 5 and 6: Pag. 30-9-2008 5
Page 7 and 8: Pag. 30-9-2008 7
Page 9 and 10: Pag. 30-9-2008 9
Page 11 and 12: 2. Chemical Concepts from DFT Funda
Page 13 and 14: Conceptual DFT (R.G. Parr, W. Yang,
Page 15 and 16: Identification of two first derivat
Page 17 and 18: • Ambiguity in the definition var
Page 19 and 20: Applications until now mostly on (g
Page 21 and 22: 3. Some applications of global and
Page 23 and 24: The Two Step Consecutive Mechanism
Page 25 and 26: • Rate Constant Evaluation • Tr
Page 27 and 28: • Local level • Softness indica
Page 29 and 30: 3.2 Lewis acid Catalysis: the role
Page 31: Transition States C m H 3Cb X 1 H 2
Page 35 and 36: 4. Towards the Inclusion of Confine
Page 37 and 38: Atoms • previous work (1992-2005)
Page 39 and 40: An atom test case: helium Radial De
Page 41 and 42: Ethylene: planar confinement • Sa
Page 43 and 44: A first try: an order of magnitude
Page 45 and 46: Epilogue: looking back at the 1979-
Page 47: 6. Acknowledgments Prof. Wilfried M

DFT Reactivity Descriptors and Catalysis - Vrije Universiteit Brussel

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