A DFT Study on the Nucleophilic Substitution of NO2-Group in 2-Nitrophthalocyanines

Alexander Yu. Tolbin,^a and Larisa G. Tomilova^a,b@

^aInstitute of Physiologically Active Compounds RAS, 142432 Chernogolovka, Russia

^bChemistry Department, Moscow State University, 119991 Moscow, Russia

^@Corresponding author E-mail: tom@org.chem.msu.ru

DOI: 10.6060/mhc2011.1.08

The reaction of NO₂-group nucleophilic substitution in mononitrophthalocyanines has been studied using quantumchemical calculations (DFT//PBE/TZ2P). The reaction is shown to proceed through the ipso-complex formation due to negligible energetic barrier (0.2 kcal/mol) of the transition state on the 2-σ–-complex → products route.

Keywords: Phthalocyanine, nucleophilic substitution, ipso-complex, DFT.

References:

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1. Phthalocyanines: Properties and Applications (Leznoff C.C., Lever A.B.P., Eds.), VCH Publishers: New York, 1989, 1993, 1996, Vols.

2. Tolbin A.Yu., Pushkarev V.E., Tomilova L.G., Zefirov N.S. Russ. Chem. Bull. 2006, 55, 1155-1158.
http://dx.doi.org/10.1007/s11172-006-0392-y

3. Tolbin A.Yu., Pushkarev V.E., Tomilova L.G., Zefirov N.S. Macroheterocycles 2009, 3, 30-32.

4. Makarov S., Litwinski C., Ermilov E.A., Suvorova O., Roder B., Woehrle D. Chem. Eur. J. 2006, 12, 1468-1474.
http://dx.doi.org/10.1002/chem.200500617

5. Mustroph H., Stollenwerk M., Bressau V. Angew. Chem. Int. Ed. 2006, 45, 2106.
http://dx.doi.org/10.1002/anie.200502820

6. Meunier B., Sorokin A. Acc. Chem. Res. 1997, 30, 470.
http://dx.doi.org/10.1021/ar960275c

7. Tolbin A.Yu., Sirotin S.V., Moskovskaya I.F., Tomilova L.G., Romanovsky B.V. Macroheterocycles 2009, 2, 261-263.

8. Tao X., Ma W., Zhang T., Zhao J. Chem. Eur. J. 2002, 8, 1321.
http://dx.doi.org/10.1002/1521-3765(20020315)8:6<1321::AID-CHEM1321>3.0.CO;2-M

9. Ali H., van Lier J.E. Chem. Rev. 1999, 99, 2379.
http://dx.doi.org/10.1021/cr980439y

10. Hu M., Brasseur N., Yildiz S.Z., van Lier J.E., Leznoff C.C. J. Med. Chem. 1998, 41, 1789-1802.
http://dx.doi.org/10.1021/jm970336s

11. Тоlbin A.Yu., Sukhorukov A.Yu., Ioffe S.L., Lobach O.A., Nosik D.N., Tomilova L.G. Mendeleev Commun. 2010, 20, 25-27.
http://dx.doi.org/10.1016/j.mencom.2010.01.010

12. Zhu X., Ai S., Chen Q., Yin H., Xu J. Electrochem. Commun. 2009, 11, 1543-1546.
http://dx.doi.org/10.1016/j.elecom.2009.05.055

13. Tolbin A.Yu., Tomilova L.G., Zefirov N.S. Russ. Chem. Rev. 2007, 76, 681-692.
http://dx.doi.org/10.1070/RC2007v076n07ABEH003698

14. Tolbin A.Yu., Pushkarev V.E., Tomilova L.G., Zefirov N.S. J. Porphyrins Phthalocyanines 2008, 12, 1187-1193.
http://dx.doi.org/10.1142/S108842460800056X

15. Tolbin A.Yu., Pushkarev V.E., Nikitin G.F., Tomilova L.G. Tetrahedron Lett. 2009, 50, 4848-4850.
http://dx.doi.org/10.1016/j.tetlet.2009.06.048

16. Pushkarev V.E., Tolbin A.Yu., Ryabova A.V., Tomilova L.G. Mendeleev Commun. 2009, 19, 24-26.
http://dx.doi.org/10.1016/j.mencom.2009.01.010

17. Tolbin A.Yu., Tomilova L.G., Zefirov N.S. Russ. Chem. Bull. 2005, 54, 2099-2103.
http://dx.doi.org/10.1007/s11172-006-0083-8

18. Erznzerhof M., Scuseria G.E. J. Chem. Phys. 1999, 110, 5029.
http://dx.doi.org/10.1063/1.478401

19. Laikov D.N., Ustynyuk Yu.A. Russ. Chem. Bull. 2005, 54, 820.
http://dx.doi.org/10.1007/s11172-005-0329-x

20. Furer V.L., Vandyukov A.E., Majoral J.P., Caminade A.M., Kovalenko V.I. Chem. Phys. 2006, 326, 417-424.
http://dx.doi.org/10.1016/j.chemphys.2006.03.004

21. Becke A.D. J. Chem. Phys. 1993, 98, 5648.
http://dx.doi.org/10.1063/1.464913

22. Lee C., Yang W., Parr R.G. Phys. Rev. 1988, B 37, 785.

23. Gordon M., http://www.msg.chem.iastate.edu/.

24. Furer V.L., Vandyukova I.I., Vandyukov A.E., Majoral J.P., Caminade A.M., Kovalenko V.I. Chem. Phys. 2009, 358, 177-183.
http://dx.doi.org/10.1016/j.chemphys.2009.01.010

25. Ostrowski S., Dobrowolski J.Cz. J. Mol. Struct. (THEOCHEM) 2010, 941, 102–106.
http://dx.doi.org/10.1016/j.theochem.2009.11.010

26. Tolbin A.Yu., Tomilova L.G., Zefirov N.S. Russ. Chem. Bull. 2005, 54, 2099-2103.
http://dx.doi.org/10.1007/s11172-006-0083-8

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