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The synaptic order: a key concept  to understand multicenter bonding Bernard Silvi Laboratoire de Chimie Théorique Université Pierre et Marie Curie 4, place Jussieu 75252 -Paris
Multicenter bond ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Origins of the concept ,[object Object],or classical Hydrogen bridges (Dilthey 1921) in contradiction with boron valence and electron count
[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
[object Object],[object Object]
Generalisation:  3c-2e  bond ,[object Object]
Generalisation:  3c-2e  bond ,[object Object]
Generalisation:  3c-4e  bonds ,[object Object]
Strengths and weaknesses ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Bonds and related concepts ,[object Object],[object Object],[object Object],[object Object]
Chemical concepts related to bonding ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Il me faut cependant avouer que la chimie proprement dite ne m’a jamais beaucoup intéressé. Pourquoi ? Peut être parce que des notions telles que celles de valence, de liaison chimique  etc., m’ont toujours semblé peu claires du point de vue conceptuel.    René Thom Paraboles et catastrophes However I have to confess that I have never been very interested in Chemistry Why? Maybe because notions such as those of valence, chemical bond, etc., seem to me unclear from a conceptual point of view
What should be a theory of the chemical bond ,[object Object],[object Object],[object Object],[object Object]
The starting point ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Topological theories of bonding ,[object Object],[object Object],[object Object],[object Object],[object Object]
[object Object],[object Object],[object Object],[object Object],[object Object],Some definitions
[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],More definitions....
A meteorological example:  V( r {  i })=-P Basin 2 Basin 1
Domains ,[object Object],[object Object],a b
Atoms  In Molecules theory ,[object Object],[object Object],[object Object],[object Object]
Back to bonding theory ,[object Object],[object Object],[object Object]
What is  ELF ? ,[object Object],[object Object],[object Object],[object Object]
Analysis: classification of basins ,[object Object],[object Object],[object Object],[object Object],[object Object],Graphical representation: isosurfaces of the function V(O) C(C) C(O) V(C, H) V(O, H) V(C, O)
Analysis of localization domains : ,[object Object],[object Object],[object Object],[object Object],parent  domain cores valence S  lone   pairs bond
Detailed diagram: Parent   domain C(O ) valence C(S) V(S) Valence   O V(S,O ) V 1 (O)+V 2 (O) V 1 (O) V 2 (0)
Hierarchy   of localization domains: complex ,[object Object],[object Object],Parent  domain HF CO2 valence C(F) C(O) valence C(O) ,  V(C,O) V(O)
Hierarchy   of localization domains: ionic pair ,[object Object],[object Object],Parent domain C(Li) F C(F) V(F)
The two processes filled-filled: 2 chemical single chemical objects (or more) complex, ionic pair, physisorption hollowed-filled: 1 chemical single chemical object molecule, ion, chemisorption
The synaptic order  ,[object Object],[object Object],[object Object]
Synaptic order: CH 3 F mon osynaptic disynaptic Protonated disynaptic
Synaptic order and chemical reactions ,[object Object]
Synaptic order and chemical reactions ,[object Object]
3c-2e  multicenter bond ,[object Object],Protonated trisynaptic
3c-2e  multicenter bond ,[object Object]
3c-2e  multicenter bond ,[object Object]
3c-2e  multicenter bond ,[object Object],0.223 0.235
3c-2e  bonds: high coordination of C ,[object Object]
Planar tetracoordinated carbons R. Choukroun, B. Donnadieu, J-S. Zhao, P. Cassoux, C. Lepetit et B. Silvi ,  Organometallics , 19,  1901-1911 (2000)
Planar pentacoordinated carbon P. v. R. Schleyer, private communication
Planar hexacoordinated carbon P. v. R. Schleyer, private communication
Metallic bond ,[object Object]
Metallic bond ,[object Object]
Metallic bond ,[object Object]
Metallic bond ,[object Object]
3c-4e  multicenter bonds ,[object Object]
Conclusions ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Nevertheless… Many forms of localization functions have been tried, and will be tried in this world of sin and woe. No one pretends that  ELF  is perfect or all-wise. Indeed, it has been the worst form of localization function except all those others that have been tried from time to time. Many forms of government have been tried, and will be tried in this world of sin and woe. No one pretends that democracy is perfect or all-wise. Indeed, it has been the worst form of government except all those others that have been tried from time to time. W. Churchill
Acknowledgements ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
That's all folks
Is a 3-center bond a bond? ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Nevertheless… Many forms of localization functions have been tried, and will be tried in this world of sin and woe. No one pretends that  ELF  is perfect or all-wise. Indeed, it has been the worst form of localization function except all those others that have been tried from time to time. Many forms of government have been tried, and will be tried in this world of sin and woe. No one pretends that democracy is perfect or all-wise. Indeed, it has been the worst form of government except all those others that have been tried from time to time. W. Churchill
Integrated conditional probability (Dobson and Savin) ,[object Object],[object Object]

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The synaptic order a key concept to understand multicenter bonding synaptic

  • 1. The synaptic order: a key concept to understand multicenter bonding Bernard Silvi Laboratoire de Chimie Théorique Université Pierre et Marie Curie 4, place Jussieu 75252 -Paris
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  • 12. Il me faut cependant avouer que la chimie proprement dite ne m’a jamais beaucoup intéressé. Pourquoi ? Peut être parce que des notions telles que celles de valence, de liaison chimique etc., m’ont toujours semblé peu claires du point de vue conceptuel. René Thom Paraboles et catastrophes However I have to confess that I have never been very interested in Chemistry Why? Maybe because notions such as those of valence, chemical bond, etc., seem to me unclear from a conceptual point of view
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  • 18. A meteorological example: V( r {  i })=-P Basin 2 Basin 1
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  • 25. Detailed diagram: Parent domain C(O ) valence C(S) V(S) Valence O V(S,O ) V 1 (O)+V 2 (O) V 1 (O) V 2 (0)
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  • 28. The two processes filled-filled: 2 chemical single chemical objects (or more) complex, ionic pair, physisorption hollowed-filled: 1 chemical single chemical object molecule, ion, chemisorption
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  • 30. Synaptic order: CH 3 F mon osynaptic disynaptic Protonated disynaptic
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  • 38. Planar tetracoordinated carbons R. Choukroun, B. Donnadieu, J-S. Zhao, P. Cassoux, C. Lepetit et B. Silvi , Organometallics , 19, 1901-1911 (2000)
  • 39. Planar pentacoordinated carbon P. v. R. Schleyer, private communication
  • 40. Planar hexacoordinated carbon P. v. R. Schleyer, private communication
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  • 47. Nevertheless… Many forms of localization functions have been tried, and will be tried in this world of sin and woe. No one pretends that ELF is perfect or all-wise. Indeed, it has been the worst form of localization function except all those others that have been tried from time to time. Many forms of government have been tried, and will be tried in this world of sin and woe. No one pretends that democracy is perfect or all-wise. Indeed, it has been the worst form of government except all those others that have been tried from time to time. W. Churchill
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  • 51. Nevertheless… Many forms of localization functions have been tried, and will be tried in this world of sin and woe. No one pretends that ELF is perfect or all-wise. Indeed, it has been the worst form of localization function except all those others that have been tried from time to time. Many forms of government have been tried, and will be tried in this world of sin and woe. No one pretends that democracy is perfect or all-wise. Indeed, it has been the worst form of government except all those others that have been tried from time to time. W. Churchill
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