1DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
Capitolo I°- CONCETTI BASE DI MOLECOLE ORGANICHE PER MATERIALI ORGANICI
DONOR, ACCEPTOR, OM, HOMO, LUMO
2DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
3DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
4DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
5DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
6DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
BENZENE
7DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
8DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
9DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
10DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
11DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
12DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
13DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
14DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
Densità di carica
Ordine di legame
Sistema ππππ neutro
Sistema ππππ eccessivo Sistema ππππ deficiente
DONOR MOLECULE ACCEPTOR MOLECULE
15
DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
Π EXCESSIVE
RING
Π DEFICIENT
RING
16DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
HOMO e LUMO: Costruzione grafica
17DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
REGOLE DI COMBINAZIONE
GRAFICA
18DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. . MilanoMilano--BicoccaBicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
Chimismo non semplicementespiegabile
19
DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. . MilanoMilano--BicoccaBicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
20
dove
DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. . MilanoMilano--BicoccaBicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
21
DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. . MilanoMilano--BicoccaBicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
22
DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. . MilanoMilano--BicoccaBicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
23
DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. . MilanoMilano--BicoccaBicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
24DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. .
MilanoMilano--BicoccaBicocca Photonics and Bio-photonics Organics Synthesis –PhoBOS
25
DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. .
MilanoMilano--BicoccaBicocca Photonics and Bio-photonics Organics Synthesis –PhoBOS
27
DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. . MilanoMilano--BicoccaBicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
28DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
+
A cosa servono gli FMO? Un caso emblematico: la reazione di DIELS ALDER. Fino agli anni 60-65 venivacatalogata come “no mechanisn reaction”. E infatti non è nè una elettrofila, nè una nucleofila nè una radicalica. Nei tardi anni 60 Woodwad e Hoffmann hannorazionalizzato questa reazione nell’ambito delleREAZIONI PERICICLICHE, una grande famiglia direazioni della quale fanno parte le reazioni dicicloaddizione (come la Diels Alder),le sigmatropiche(spostamento di atomi di idrogeno e/residui alchilci e/oaromatici lungo una catena insatura), le cheletropiche, ecc. Può essere razionalizzata con gli FMO.
29
DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
30DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
Effetto sostituente sulla reazione di Diels Alder
I fatti:
Perchè?
31DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
Come variano gli HOMO e i Lumo con I sostituenti?
32DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
33DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
La Diels
Alder
invertita
34DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
Gli Orbitali Molecolari di frontiera (FMO) proposti da Fukui (Nobel nel ’72) hanno il pregio di ricomprendere il contributo diWoodward e Hoffmann (Conservazione della simmetria degliorbitali molecolari – 1966-68 – entrambi Nobel)) e la teoria diPearson e Dillon (Acidi e Basi ovvero nucleofili e o elettrofili duri
e molli) proposta indipendentemente attorno al ’68. Gli FMO sono quinindi la teoria unitaria del comportamentochimico organico racchiusa dall’equazione di
Klopman-Salem.
35DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
36DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
37DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
38DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS
39DeptDept. . MaterialsMaterials ScienceScience, , UnivUniv. Milano. Milano--Bicocca Bicocca Photonics and Biophotonics Organics Synthesis - PhoBOS