Electrophilicity and Nucleophilicity of Commonly Used. Aldehydes

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1 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2014 ESI-1 Supporting Information (ESI-1) Electrophilicity and Nucleophilicity of Commonly Used Aldehydes Sanjay Pratihar * Department of Chemical Sciences, Tezpur University, Napaam,784028, Asam, India spratihar29@gmail.com, spratihar@tezu.ernet.in

2 Table of contents: Page No Experimental Section: 1 Theoretical Background: 1-3 Table S1. Absorbane band ( max ) of six different para substituted benzaldehyde 3 Figure S1: Hammett plot of log(k Y /k H ) versus σ p for KMnO4 oxidation of six different para substituted aldehyde 4 Figure S2: Hammett plot of log(k Y /k H ) versus σ p for NABH 4 reduction of six different para substituted aldehyde Table S2. Pseudo first order rate constant values of KMnO 4 Oxidation of five different para substituted benzaldehydes 5 Table S3. Pseudo first order rate constant values of NaBH 4 reduction of five different para substituted benzaldehydes 5 Theoretical Section 5 4 Table S4. Optimized structure along with some important bond distance of aldehyde MnO4- intermediates. Table S5. Optimized Tranisition state (TS) structure along with some important bond distance of KMnO 4 oxidation reaction. Table S6. HOMO, LUMO,Hardness (,Chemical Potential ( elecytrophilicity (E), Nucleophilicity (N) values of various mono, di, and tri-substituted aldehydes calculated at B3LYP/6-311+G** level of theory in gas phase. Table S7. Experimental and theoretical Nucleophilicity(N), Electrophilicity (E),and Net E of various aldehyde from kinetics and theoretical (gas phase calculation in MI) analysis Fig. S3. Theoretical nucleophilicity in acetonitrile versus Experimental nucleophilicity plot of various para substituted benzaldehydes in three different methods Fig. S4. Theoretical electrophilicity in acetonitrile versus Experimental electrophilicity plot of various para substituted benzaldehydes in three different methods Table S8. HOMO, LUMO, Hardness (,Chemical Potential ( elecytrophilicity (E),and Nucleophilicity (N) values of various mono, di, and tri-substituted aldehydes calculated at B3LYP/6-311+G** level of theory in acetonitrile in method I. Fig. S5. Theoretical nucleophilicity in method I versus Experimental nucleophilicity plot of various aldehyde

3 Fig. S6. Theoretical electrophilicity in method I versus experimental electrophilicity plot of various para substituted benzaldehydes in three different methods Table S9 Table S9. Electrophilicity of five different aldehyde in this method and by mayr et al. Fig. S7. Experimental electrophilicity in method versus experimental electrophilicity by Mayr et al. Table S10. Ln(K/T) versus (1/T) plot for the determination of activation parameter for KMnO 4 oxidation reaction of five different para-substituted benzaldehyde. Table S11. Ln(K/T) versus (1/T) plot for the determination of activation parameter for NaBH 4 reduction of five different para-substituted benzaldehyde. Table S12. Ln(A) versus time plot for the determination of rate constant (k) for NaBH 4 reduction of six different para-substituted benzaldehyde at 298 K. Table S13. Ln(A) versus time plot for the determination of rate constant (k) for NaBH 4 reduction of Five different para-substituted benzaldehyde at 291 K. Table S14. Ln(A) versus time plot for the determination of rate constant (k) for NaBH 4 reduction of Five different para-substituted benzaldehyde at 283 K. Table S15. Ln(A) versus time plot for the determination of rate constant (k) for NaBH 4 reduction of Five different para-substituted benzaldehyde at 275 K Table S16. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of Five different para-substituted benzaldehyde at 275 K. Table S17. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of Five different para-substituted benzaldehyde at 285 K. Table S18. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of Five different para-substituted benzaldehyde at 298 K. Table S19. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of Five different para-substituted benzaldehyde at 309 K. Table S20. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of Five different para-substituted benzaldehyde at 321 K. Table S21. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of Five different para-substituted benzaldehyde at 333 K. Table S22. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of six different aldehyde at 298 K Table S23. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of Five different aldehyde at 298 K Table S24. Ln(A) versus time plot for the determination of rate constant (k) for 31

4 NaBH 4 reduction of six different benzaldehyde at 298 K. References 32

5 Experimental Section: Materials and Instruments: Double distilled water was used throughout the experiments. Degassing of oxygen in water and acetonitrile has been done with bubbling of argon for 30 minute. Acetonitrile, aldehydes, and KMnO 4 were of AR grade. All the reagents were used without further purification. All UV-visible absorption spectra were recorded in a double beam digital spectrophotometer attached with a chiller. UV-vis study for KMnO 4 Oxidation of aldehydes: At first an aqueous homogeneous solution of KMnO 4 ( M) in double distilled oxygen free water has been prepared for the study. In another set, 5 ml aldehyde stock solution ( M) has been prepared in pre-distilled oxygen free acetonitrile. Then 200 µl of aldehyde solution has been mixed with KMnO 4 solution ( M) in a UV-cuvette to record the progress of the reaction. The progress of the reaction has been accounted from a steady decrease of all the four absorbance maxima at specified band (506, 525, 545, and 566 nm) positions (Figure 1). All the rate measurement for KMnO 4 oxidation of aldehyde has been done with time scan option at fixed absorbance (545 nm band of KMnO 4 ). UV-vis study for NaBH 4 reduction of aldehydes: For monitoring the reduction kinetics of aldehydes, NaBH 4 solution (20 M) in double distilled oxygen free water has been prepared. The aqueous NaBH 4 solution is admixed with 100 µl distilled oxygen free acetonitrile stock solution ( M) of corresponding aldehyde. All the rate measurement for NaBH 4 reduction of aldehyde has been done with time scan option at fixed absorbance band of a particular aldehyde. Theoretical Background: Global reactivity descriptors are defined for the system as a whole. Recently electrophilicity has been defined by Parr et al. 7a as the energy of stabilization of a chemical species when it attains an additional fraction of electronic charge from the environment. The global electrophilicity index

6 is defined as = /2 where is the electronic chemical potential 1 and is the chemical hardness. 2 In an important contribution, Gazquez et al. 9 have defined electrodonating power ( ) as 2 I 2( I A) 2 (3I A) and (1) 16( I A) Note that according to this definition, a low value of signifies a better electron donor. In the present work nucleophilicity has been defined as the inverse of electrodonating power (10/ ) in order to equate with the general notion that more is better. They also described electroaccepting power ( ) as 2 A 2( I A) 2 ( I 3A) and (2) 16( I A) Later on, Ayers et. al. introduced two sets of different equation from the IP and EA for both the electrophilicity and nucleophilicity as 8 N (3I 8( I 2 A) A) 2 ( I A) and E (3) 8( I A) The electronic chemical potential and the chemical hardness have to be known for the calculation of electrophilicity (E) and nucleophilicity (N) index. The electronic chemical potential is the negative of electronegativity χ, is defined for an N-electron system with external potential v(r) and total energy E as the partial derivative of the energy to the number of electrons at constant external potential and in absence of a magnetic field: 3 E I A N 2 V (r) 2

7 where I and A are the vertical ionization energy and electron affinity, respectively. These two quantities were calculated in Gaussian 03 program 4 by using the B3LYP methods and G** as basis set. Hardness is defined as the corresponding second derivative as proposed by Parr and Pearson E 2 2 N ( I A) v( r) It is now common to exclude the factor ½ in the above definition. In this paper we calculated the chemical hardness as the difference between the vertical ionization energy I and electron affinity A. Where Ionization potential (IP) and A E LUMO = Electron affinity (EA) The following absorbance band of aldehydes have been chosen for rate measurement of NaBH4 reduction of aldehyde (Table S1). Table S1. Absorbane band ( max ) of six different para substituted benzaldehydes. Aldehyde max (nm) 4- (dimethyl amino) benzaldehyde Methoxy Benzaldehyde Methyl Benzaldehyde 263 Benzaldehyde Bromo Benzaldehyde Chloro Benzaldehyde 258 3

8 Figure S1: Hammett plot of log(k Y /k H ) versus σ p for KMnO 4 oxidation of six different para substituted aldehyde. Figure S2: Hammett plot of log(k Y /k H ) versus σ p for NABH 4 reduction of six different para substituted aldehyde. 4

9 Table S2. Pseudo first order rate constant values of KMnO 4 Oxidation of five different para substituted benzaldehydes. Temperature Cl (sec -1 ) Br (sec -1 ) H (sec -1 ) OMe (sec -1 ) NMe 2 (sec -1 ) 275 K K K K K K Table S3. Pseudo first order rate constant values of NaBH 4 reduction of five different para substituted benzaldehydes. Temperature Cl (sec -1 ) Br (sec -1 ) H (sec -1 ) OMe (sec -1 ) NMe 2 (sec -1 ) 275 K K K K Theoretical Section: The ground state geometry optimizations of all the aldehydes were performed using GAUSSIAN at B3LYP level of theory. All the atoms are treated with G(d,p) basis set. Geometries of all species studied were fully optimized, and they were characterized as true intermediates on the potential energy surface by the absence of imaginary frequencies, after frequency calculation on the optimized geometries. During the reaction path analysis The transition state (TS) model of KMnO4 oxidation reaction has been analyzed at B3LYP level of theory. For Manganese Effective core potential (ECP) along with valence basis sets (LANL2DZ) was used, while for other atoms G** basic set was used. 5

10 Table S4. Optimized structure along with some important bond distance of aldehyde MnO4- intermediates. 6

11 Table S5. Optimized Tranisition state (TS) structure along with some important bond distance of KMnO 4 oxidation reaction. 7

12 Table S6. HOMO, LUMO,Hardness (,Chemical Potential ( elecytrophilicity (E), Nucleophilicity (N) values of various mono, di, and tri-substituted aldehydes calculated at B3LYP/6-311+G** level of theory. Compound HOMO (ev) LUMO (ev) E N 2-Nitro benzaldehyde Nitro benzaldehyde Cyano benzaldehyde chloroisophthalaldehyde nitro-1H-indole-3-carbaldehyde phthalaldehyde Acetyl benzaldehyde formyl benzonitrile formyl benzoic acid ,4-dichloropicolinaldehyde Ethylglyoxalate formyl benzonitrile chloronicotinaldehyde Trifluromethyl benzaldehyde Methyl-4-formylbenzoate ,4,5-trifluorobenzaldehyde Nitro benzaldehyde chloropicolinaldehyde isophthalaldehyde ,3-dichlorobenzaldehyde chlorofuran-2-carbaldehyde Acetyl benzaldehyde ,6-dichlorobenzaldehyde formyl benzoic acid phenyl propynal formyl benzoic acid Cinamaldehyde Acetyl benzaldehyde Bromo benzaldehyde Chloro benzaldehyde Methyl-3-formylbenzoate Bromo benzaldehyde Chloro aldehyde picolinaldehyde Fluro benzaldehyde Methyl-2-formylbenzoate Bromo benzaldehyde (thiophen-3-yl) benzaldehyde

13 biphenyl-4-carbaldehyde Fluro benzaldehyde Chloro benzaldehyde Biphenyl-2-carbaldehyde thiophene-2-carbaldehyde naphthaldehyde Fluro benzaldehyde chloro-3,4-dihydroxybenzaldehyde Benzaldehyde Methyl benzaldehyde tert-butyl-2-hydroxybenzaldehyde hydroxy benzaldehyde furan-2-carbaldehyde (naphthalen-2-yl)benzaldehyde methyl benzaldehyde chloro-4-hydroxy- 5-methoxybenzaldehyde Methyl benzaldehyde Methoxy benzaldehyde Ethyl Benzaldehyde Mercapto Benzaldehyde Propyl benzaldehyde formylphenylboronic acid Methoxy benzaldehyde thiophene-3-carbaldehyde amino benzaldehyde ,4,5-trimethoxybenzaldehyde ,4-dihydroxybenzaldehyde Hydroxy benzaldehyde furan-3-carbaldehyde Methoxy benzaldehyde chloro-1H-indole-3-carbaldehyde Formaldehyde (dimethylamino) benzaldehyde hydroxy-3-methoxybenzaldehyde (dimethylamino) benzaldehyde Amino benzaldehyde Phenyl acetaldehyde (dimethylamino) benzaldehyde Phenyl propanal Acetaldehyde Heptanal

14 Table S7. Experimental and theoretical Nucleophilicity(N), Electrophilicity (E),and Net E of various aldehyde from kinetics and theoretical (gas phase calculation in MI) analysis Compound E (theo) N (theo) N (exp) E (exp) Net E (exp) 2-Nitro benzaldehyde Nitro benzaldehyde Cyano benzaldehyde chloroisophthalaldehyde formyl benzonitrile phthalaldehyde Acetyl benzaldehyde formyl benzoic acid ,4-dichloropicolinaldehyde Ethylglyoxalate nitro-1H-indole-3-carbaldehyde formyl benzonitrile Trifluromethyl benzaldehyde Nitro benzaldehyde ,4,5-trifluorobenzaldehyde chloronicotinaldehyde Methyl-4-formylbenzoate chloropicolinaldehyde isophthalaldehyde ,3-dichlorobenzaldehyde chlorofuran-2-carbaldehyde Acetyl benzaldehyde formyl benzoic acid ,6-dichlorobenzaldehyde formyl benzoic acid Phenyl propynal Acetyl benzaldehyde Methyl-3-formylbenzoate Chloro benzaldehyde Chloro aldehyde Cinamaldehyde Fluro benzaldehyde Bromo benzaldehyde Bromo benzaldehyde picolinaldehyde Bromo benzaldehyde Fluro benzaldehyde Chloro benzaldehyde

15 Methyl-2-formylbenzoate thiophene-2-carbaldehyde biphenyl-4-carbaldehyde Fluro benzaldehyde Biphenyl-2-carbaldehyde (thiophen-3-yl) benzaldehyde Benzaldehyde naphthaldehyde Methyl benzaldehyde furan-2-carbaldehyde chloro-3,4-dihydroxybenzaldehyde methyl benzaldehyde hydroxy benzaldehyde tert-butyl-2-hydroxybenzaldehyde Methyl benzaldehyde Ethyl Benzaldehyde Propyl benzaldehyde formylphenylboronic acid thiophene-3-carbaldehyde chloro-4-hydroxy-5-methoxybenzaldehyde Methoxy benzaldehyde Methoxy benzaldehyde Formaldehyde (naphthalen-2-yl)benzaldehyde Mercapto Benzaldehyde Hydroxy benzaldehyde furan-3-carbaldehyde ,4-dihydroxybenzaldehyde amino benzaldehyde ,4,5-trimethoxybenzaldehyde Methoxy benzaldehyde chloro-1H-indole-3-carbaldehyde hydroxy-3-methoxybenzaldehyde (dimethylamino) benzaldehyde Phenyl acetaldehyde Amino benzaldehyde Acetaldehyde Phenyl propanal (dimethylamino) benzaldehyde Heptanal (dimethylamino) benzaldehyde

16 Fig. S3. Theoretical nucleophilicity in acetonitrile versus Experimental nucleophilicity plot of various para substituted benzaldehydes in three different methods Fig. S4. Theoretical electrophilicity in acetonitrile versus Experimental electrophilicity plot of various para substituted benzaldehydes in three different methods 12

17 Table S8. HOMO, LUMO, Hardness (,Chemical Potential ( elecytrophilicity (E),and Nucleophilicity (N) values of various mono, di, and tri-substituted aldehydes calculated at B3LYP/6-311+G** level of theory in acetonitrile in method I. Compound HOMO LUMO E N 2,4,5-trifluorobenzaldehyde Nitro benzaldehyde Nitro benzaldehyde picolinaldehyde phthalaldehyde Ethylglyoxalate chloroisophthalaldehyde ,4-dichloropicolinaldehyde formyl benzonitrile Phenyl propynal Nitro benzaldehyde chloronicotinaldehyde chloropicolinaldehyde ,3-dichlorobenzaldehyde formyl benzoic acid ,6-dichlorobenzaldehyde Acetyl benzaldehyde ,4,5-trimethoxybenzaldehyde Cinamaldehyde isophthalaldehyde Methyl-2-formylbenzoate Acetyl benzaldehyde Biphenyl-2-carbaldehyde biphenyl-4-carbaldehyde chlorofuran-2-carbaldehyde formyl benzonitrile thiophene-3-carbaldehyde (thiophen-3-yl) benzaldehyde formyl benzoic acid Bromo benzaldehyde Methyl-3-formylbenzoate Chloro aldehyde Cyano benzaldehyde Acetyl benzaldehyde Fluro benzaldehyde Chloro benzaldehyde naphthaldehyde

18 3-Fluro benzaldehyde formyl benzoic acid thiophene-2-carbaldehyde Methyl-4-formylbenzoate Methyl benzaldehyde chloro-3,4-dihydroxybenzaldehyde Methoxy benzaldehyde methyl benzaldehyde tert-butyl-2-hydroxybenzaldehyde formylphenylboronic acid furan-2-carbaldehyde hydroxy benzaldehyde Methoxy benzaldehyde (naphthalen-2-yl)benzaldehyde chloro-4-hydroxy-5-methoxybenzaldehyde chloro-1H-indole-3-carbaldehyde Trifluromethyl benzaldehyde amino benzaldehyde (dimethylamino) benzaldehyde ,4-dihydroxybenzaldehyde hydroxy-3-methoxybenzaldehyde (dimethylamino) benzaldehyde Chloro benzaldehyde furan-3-carbaldehyde Bromo benzaldehyde Formaldehyde nitro-1H-indole-3-carbaldehyde Fluro benzaldehyde Methyl benzaldehyde Ethyl Benzaldehyde Propyl benzaldehyde Mercapto Benzaldehyde Benzaldehyde Phenyl acetaldehyde Acetaldehyde Phenyl propanal Hydroxy benzaldehyde Heptanal Methoxy benzaldehyde Amino benzaldehyde (dimethylamino) benzaldehyde Bromo benzaldehyde

19 Fig. S5. Theoretical nucleophilicity in method I versus Experimental nucleophilicity plot of various aldehyde. Fig. S6. Theoretical electrophilicity in method I versus experimental electrophilicity plot of various para substituted benzaldehydes in three different methods 15

20 Table S9. Electrophilicity of five different aldehyde in this method and by mayr et al. Aldehyde Electrophilicity (in this Electrophilicity (Mayr et al.) 5 method) 3-chloro benzaldehyde fluro benzaldehyde methoxy benzaldehyde fluro benzaldehyde Benzaldehyde Fig. S7. Experimental electrophilicity in method versus experimental electrophilicity by Mayr et al. 16

21 Table S10. Ln(K/T) versus (1/T) plot for the determination of activation parameter for KMnO 4 oxidation reaction of five different para-substituted benzaldehyde. 17

22 Table S11. Ln(K/T) versus (1/T) plot for the determination of activation parameter for NaBH 4 reduction of five different para-substituted benzaldehyde. 18

23 Table S12. Ln(A) versus time plot for the determination of rate constant (k) for NaBH 4 reduction of six different para-substituted benzaldehyde at 298 K. 19

24 Table S13. Ln(A) versus time plot for the determination of rate constant (k) for NaBH 4 reduction of Five different para-substituted benzaldehyde at 291 K. 20

25 Table S14. Ln(A) versus time plot for the determination of rate constant (k) for NaBH 4 reduction of Five different para-substituted benzaldehyde at 283 K. 21

26 Table S15. Ln(A) versus time plot for the determination of rate constant (k) for NaBH 4 reduction of Five different para-substituted benzaldehyde at 275 K. 22

27 Table S16. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of Five different para-substituted benzaldehyde at 275 K. 23

28 Table S17. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of Five different para-substituted benzaldehyde at 285 K. 24

29 Table S18. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of Five different para-substituted benzaldehyde at 298 K. 25

30 Table S19. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of Five different para-substituted benzaldehyde at 309 K. 26

31 Table S20. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of Five different para-substituted benzaldehyde at 321 K. 27

32 Table S21. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of Five different para-substituted benzaldehyde at 333 K. 28

33 Table S22. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of six different aldehyde at 298 K. 29

34 Table S23. Ln(A) versus time plot for the determination of rate constant (k) for KMnO 4 oxidation of Five different aldehyde at 298 K. 30

35 Table S24. Ln(A) versus time plot for the determination of rate constant (k) for NaBH 4 reduction of six different benzaldehyde at 298 K. 31

36 1 Parr, R. G.; Donnelly, R. A.; Levy, M.; Palke, W. E. J. Chem. Phys. 1978, 68, Parr, R. G.; Pearson, R. G. J. Am. Chem. Soc. 1983, 105, Parr, R. G.; Donnelly, R. A.; Levy, M.; Palke, W. E. Journal of Chemical Physics 1978, 68, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, References O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Gaussian, Inc.: Wallingford, CT, R. Appel, H. Mayr, J. Am. Chem. Soc. 2011, 133,

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