Summary.
Equilibrium constants and molar extinction coefficients for 1:1 charge-transfer complexes between 2-hydroxyaniline (HA), 5-chloro-2-hydroxyaniline (CHA), and 4-bromo-2,6-dimethylaniline (BMA) as donors and iodine, as a typical σ-acceptor were determined spectrophotometrically in chloroform, dichloromethane, and carbontetrachloride solutions. Spectral characteristics and formation constants are discussed in terms of donor molecular structure and solvent polarity. The stoichiometry of the complexes was established to be 1:1. For this purpose, optical data were subjected to the form of the Rose-Drago equation for 1:1 equilibria. Electronic absorption spectra of the studied anilines were measured in different solvents. Spectral data were reported and band maxima were assigned to the appropriate molecular orbital transitions (π–π* and n–π* electronic transition). Solvent effects on the electronic transitions were discussed. Optimized geometry of the studied anilines was obtained at B3LYP/6-31 + G(d). The effect of the electronic factors of the substituents on the geometrical parameters of the ring has been explored. Geometrical values of the ring deviate from the regular hexagonal ring. Intramolecular H-bonds in HA and CHA have been computed at B3LYP/6-31 + G(d) and MP2/6-31 + G(d) levels. The H-bonding distance was calculated to be 2.105 Å in HA and 2.127 Å in CHA.
Similar content being viewed by others
References
N Haga H Nakajima H Takayanagi K Tokumaru (1998) J Org Chem 63 5372 Occurrence Handle1:CAS:528:DyaK1cXkvFKgsbk%3D Occurrence Handle10.1021/jo9801824
RS Mulliken WB Person (1969) Molecular Complexes: A Lecture and Reprint Volume Wiley & Sons New York
M Kroll (1968) J Am Chem Soc 90 1097 Occurrence Handle1:CAS:528:DyaF1cXptFGjtQ%3D%3D Occurrence Handle10.1021/ja01007a001
MJS Dewar AR Lepley (1961) J Am Chem Soc 83 4560 Occurrence Handle1:CAS:528:DyaF38XntFSitA%3D%3D Occurrence Handle10.1021/ja01483a015
JL Lippert MW Hanna PJ Trotter (1969) J Am Chem Soc 91 4035 Occurrence Handle1:CAS:528:DyaF1MXkvVCks7g%3D Occurrence Handle10.1021/ja01043a003
K Morokuma (1977) Accounts Chem Res 10 294 Occurrence Handle1:CAS:528:DyaE2sXkslensb4%3D Occurrence Handle10.1021/ar50116a004
I Røeggen T Dahe (1992) J Am Chem Soc 114 511 Occurrence Handle10.1021/ja00028a017
T Matsuo O Higuchi (1968) Bull Chem Soc Jpn 41 518 Occurrence Handle1:CAS:528:DyaF1cXhtVymsL4%3D Occurrence Handle10.1246/bcsj.41.518
BM Shimkin AV Triolo (1969) Prog ExD Tumor Res 11 1 Occurrence Handle1:CAS:528:DyaE3MXht1alt7Y%3D
LM Budni RS Magadum (1992) Spectrochimica Acta A 48 1505 Occurrence Handle10.1016/0584-8539(92)80159-T
VT Kumar CT Singh G Venkateshwarlu (2001) Indian J Chem 40 622
S Bhattacharya M Baneriee (2001) Spectrochim Acta 57 2409 Occurrence Handle1:STN:280:DC%2BD38%2FjvVWgsQ%3D%3D Occurrence Handle10.1016/S1386-1425(01)00427-9
M Bugeanu EmV Sahini (1988) Revue Roumaine de Chimie 33 75 Occurrence Handle1:CAS:528:DyaL1MXlvFCjs7o%3D
J Csaszar MN Bizony (1990) Acta Physica et Chem 36 66 Occurrence Handle1:CAS:528:DyaK38XkvFylsr4%3D
YO Kwon HU Paek RE Kim (1991) Korean Chem Soc 35 343 Occurrence Handle1:CAS:528:DyaK3MXlsFyhsbg%3D
H Kusakawa S Nishizaki (1964) Nippon Kajakuzasshi 85 241 Occurrence Handle1:CAS:528:DyaF2cXktFOltrc%3D
AMS Andrabi (2002) Indian J Chem 41 2306
PS Sibley LR Campbell BH Silber (1995) J Phys Chem 99 5274 Occurrence Handle1:CAS:528:DyaK2MXkvVWqsb0%3D Occurrence Handle10.1021/j100015a007
S Bhattacharya KS Nayak S Chattopadhyay M Banerjee KA Mukherjee (2002) J Phys Chem 106 6710 Occurrence Handle1:CAS:528:DC%2BD38XkvFaqtrk%3D
F Bertinelli P Palmieri A Brillante C Taliani (1977) Chem Phys 25 333 Occurrence Handle1:CAS:528:DyaE1cXhtl2gtw%3D%3D Occurrence Handle10.1016/0301-0104(77)85143-4
G Bendazzoli F Bertinelli P Palmieri C Taliani (1976) Chem Phys 16 319 Occurrence Handle1:CAS:528:DyaE2sXhtl2itL4%3D Occurrence Handle10.1016/0301-0104(76)87027-9
DA Taneja PK Srivastava CM Gupta (1973) J Chinese Chem Soc (Taipei, Taiwan) 20 95 Occurrence Handle1:CAS:528:DyaE3sXksVWmtbY%3D
B Scheuer-Lamalle G Durocher (1976) Canadian J Spectroscopy 21 165 Occurrence Handle1:CAS:528:DyaE2sXhtlyqsLg%3D
AA Aly AA Hassann SY Mohamed EA Mourad H Hopf (1992) Monatshefte fuer Chemie 123 179 Occurrence Handle1:CAS:528:DyaK38XitFeqsb4%3D
B Ying L Hong (1993) Zhongshan Daxue Xuebao, Ziran Kexueban 32 53 Occurrence Handle1:CAS:528:DyaK2cXlsFOru7g%3D
P Pal A Saha KA Mukherjee CD Mukherjee (2004) Spectrochim Acta 60 167 Occurrence Handle10.1016/S1386-1425(03)00189-6 Occurrence Handle1:CAS:528:DC%2BD3sXps1Sisro%3D
WB Tzeng K Narayanan (1998) J Mol Struct 446 93 Occurrence Handle1:CAS:528:DyaK1cXitVCht7g%3D Occurrence Handle10.1016/S0022-2860(97)00402-X
JV Prasad SB Rai SN Thakur (1989) Chem Phys Lett 164 629 Occurrence Handle1:CAS:528:DyaK3cXoslWjtw%3D%3D Occurrence Handle10.1016/0009-2614(89)85272-8
KM Gough BR Henry (1983) J Phys Chem 87 3804 Occurrence Handle1:CAS:528:DyaL3sXltlSmt7k%3D Occurrence Handle10.1021/j100243a003
MK Ahmed BR Henry (1986) J Phys Chem 90 1737 Occurrence Handle1:CAS:528:DyaL28Xhs1Orurk%3D Occurrence Handle10.1021/j100400a002
Y Mizugai M Katayama N Nakayama (1981) J Am Chem Soc 103 5061 Occurrence Handle1:CAS:528:DyaL3MXkvFKgtbk%3D Occurrence Handle10.1021/ja00407a018
MS Dewar PJ Grisdale (1962) J Am Chem Soc 84 3539 Occurrence Handle1:CAS:528:DyaF3sXosVer Occurrence Handle10.1021/ja00877a023
GD Lister JK Tyler JH Hog NW Larsen (1974) J Mol Struct 23 253 Occurrence Handle1:CAS:528:DyaE2MXkt1Ckug%3D%3D Occurrence Handle10.1016/0022-2860(74)85039-8
G Shultz G Portalone F Ramondo A Domenicano I Hargittai (1996) Struct Chem 7 59 Occurrence Handle10.1007/BF02275450
M Fukuyo K Hirotsu T Higuchi (1982) Acta Cryst B 38 640 Occurrence Handle10.1107/S056774088200363X
MA Palafox JL Nunez M Gil (2002) J Mol Struct (Theochem) 593 101 Occurrence Handle10.1016/S0166-1280(02)00319-6
WB Zeng K Narayanan KC Shieh CC Tung (1998) J Mol Struct (Theochem) 428 231 Occurrence Handle10.1016/S0166-1280(97)00286-8
ME Vaschetto BA Retamal AP Monkman (1998) J Mol Struct (Theochem) 468 254
L Santos E Martinez B Ballesteros J Sanchez (2000) Spectrochim Acta A 56 1905 Occurrence Handle10.1016/S1386-1425(00)00248-1
M Kurta M Yurdakulb S Yurdakul (2004) J of Mol Struct (Theochem) 711 25 Occurrence Handle10.1016/j.theochem.2004.07.034 Occurrence Handle1:CAS:528:DC%2BD2cXhtVClsLjI
A Altun K Golcuk M Kumru (2003) J Mol Struct 625 17 Occurrence Handle1:CAS:528:DC%2BD3sXis1Gkt70%3D Occurrence Handle10.1016/S0166-1280(02)00698-X
WB Tzeng K Narayanan JL Lin CC Tung (1999) Spectrochim Acta 55A 153 Occurrence Handle1:CAS:528:DyaK1MXjs1OjsQ%3D%3D
Sandorfy C (1964) Electronic Spectra and Quantum Chemistry, JN Prentice Hall
HA Benesi JH Hildebrand (1949) J Am Chem Soc 71 1703 Occurrence Handle10.1021/ja01176a030
NJ Rose RS Drago (1959) J Am Chem Soc 81 6138 Occurrence Handle1:CAS:528:DyaF3cXltlOhug%3D%3D Occurrence Handle10.1021/ja01532a009
L Meng-Sheng L Yun DP Vernon S Steve (2003) J Phys Chem A 107 8939 Occurrence Handle10.1021/jp034985t Occurrence Handle1:CAS:528:DC%2BD3sXns1Ggtbo%3D
CC Thompson SuffixJr PAD Demaine (1963) J Am Chem Soc 85 3096 Occurrence Handle1:CAS:528:DyaF3sXks1yls7Y%3D Occurrence Handle10.1021/ja00903a010
VG Krishna M Chowdhury (1963) J Am Chem Soc 67 1067 Occurrence Handle1:CAS:528:DyaF3sXnslWrsg%3D%3D
Furniss BS, Hannaford AJ, Rogers V, Smith PWG, Tatchell AR (1978) “Text Book of Practical Organic Chemistry” 4th edition, Longman Group Ltd
T Kubota (1965) J Am Chem Soc 87 458 Occurrence Handle1:CAS:528:DyaF2MXjsVSmuw%3D%3D Occurrence Handle10.1021/ja01081a012
VG Krishna BB Bhowmik (1968) J Am Chem Soc 90 1700 Occurrence Handle1:CAS:528:DyaF1cXkt1KltL8%3D Occurrence Handle10.1021/ja01009a004
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Zakrzewski VG, Montgomery JA, Stratmann RE, Burant JC, Dapprich S, Millam JM, Daniels AD, Kudin KN, Strain MC, Farkas O, Tomasi J, Barone V, Cossi M, Cammi R, Mennucci B, Pomelli C, Adamo C, Clifford S, Ochterski J, Petersson GA, Ayala PY, Cui Q, Morokuma K, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Cioslowski J, Ortiz JV, Baboul AG, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Gomperts R, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Gonzalez C, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Andres JL, Gonzalez C, Head-Gordon M, Replogle ES, Pople JA (1998) Gaussian 98, revision A7; Gaussian: Pittsburgh PA
AD Becke (1993) J Chem Phys 98 5648 Occurrence Handle1:CAS:528:DyaK3sXisVWgtrw%3D Occurrence Handle10.1063/1.464913
BA Miehlich HS Savin H Preuss (1989) Chem Phys Lett 157 200 Occurrence Handle1:CAS:528:DyaL1MXkvVCgsL4%3D Occurrence Handle10.1016/0009-2614(89)87234-3
M Head-Gordon JA Pople MJ Frisch (1988) Chem Phys Lett 153 503 Occurrence Handle1:CAS:528:DyaL1MXhs1SmtLo%3D Occurrence Handle10.1016/0009-2614(88)85250-3
MJ Frisch M Head-Gordon AJ Pople (1990) Chem Phys Lett 166 275 Occurrence Handle1:CAS:528:DyaK3cXhs1Giu7g%3D Occurrence Handle10.1016/0009-2614(90)80029-D
MJ Frisch M Head-Gordon JA Pople (1990) Chem Phys Lett 166 281 Occurrence Handle1:CAS:528:DyaK3cXhs1Giu7k%3D Occurrence Handle10.1016/0009-2614(90)80030-H
M Head-Gordon T Head-Gordon (1994) Chem Phys Lett 220 122 Occurrence Handle1:CAS:528:DyaK2cXjtV2qsLc%3D Occurrence Handle10.1016/0009-2614(94)00116-2
S Saebo J Almlof (1989) Chem Phys Lett 154 83 Occurrence Handle1:CAS:528:DyaL1MXhsVWktrg%3D Occurrence Handle10.1016/0009-2614(89)87442-1
Author information
Authors and Affiliations
Corresponding author
Additional information
Abstracted from her M.Sc. thesis
Rights and permissions
About this article
Cite this article
El-Gogary, T., Diab, M. & El-Tantawy, S. Spectroscopic and Quantum Mechanical Studies of Substituted Anilines and their Charge-Transfer Complexes with Iodine in Different Solvents. Monatsh. Chem. 137, 1027–1042 (2006). https://doi.org/10.1007/s00706-006-0511-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00706-006-0511-3