Density Functional Theory Studies on the t-Butoxyl Radical Mediated Hydrogen Atom Transfer Reactions†

doi:10.7503/cjcu20150326

Abstract

Abstract:

The reaction mechanisms of hydrogen abstractions from carbon by the t-butoxyl radical were investigated with several density functional theory(DFT) methods, such as CAM-B3LYP, M062x and wB97x. The results show that most of these reactions are dominated more by entropic than by enthalpic factor. The activation free energy barriers were calculated with both gas-phase translational entropy and solution translational entropy, in which those from ideal gas-phase translational entropy(output of Gaussian job) were much higher than the experimental estimations. It has been verified that free-energy barriers of amines and hydrocarbons reactions generated from solution translational entropies are close to the experimental measurements, but all these methods predict a little low free-energy barriers for alcohols and ethers reactions.

Key words: t-Butoxyl radical, Hydrogen abstraction, Free-energy barriers in solution, Rate constant

CLC Number:

O641

TrendMD:

LI Yue, FANG Decai. Density Functional Theory Studies on the t-Butoxyl Radical Mediated Hydrogen Atom Transfer Reactions^†[J]. Chem. J. Chinese Universities, 2015, 36(10): 1954.

Figures/Tables 6

References 40

[1]	Walling C., Jacknow B. B., J. Am.Chem. Soc., 1960, 82, 6108—6112
[2]	Walling C., McGuiness J. A., J. Am.Chem. Soc., 1969, 91(8), 2053—2058
[3]	Carter W. P. L., Darnall K. R., Lioyd A. C., Chem. Phys. Lett., 1976, 42(1), 22—27
[4]	Adam W., Grimm G. N., Saha-Moeller C. R., Dall A. F., Miolo G., Daniela V., Chem. Res. Toxicology., 1998, 11, 1089—1097
[5]	Adam W., Marquardt S., Kemmer D., Saha-Moeller C. R., Schreier P., Org. Lett., 2002, 4, 225—228
[6]	Mahler H. C., Schulz I., Adam W., Grimm G. N., Saha-Moeller C. R., Epe B., Mutation Research, 2001, 46, 289—299
[7]	Jones C. M., Burkitt M. J., J. Am. Chem. Soc., 2003, 125, 6946—6954
[8]	Lindsay S. J. R., Nagatomi E., Stead A., Waddington D. J., Beviere S. D., J. Chem. Soc., Perkin Trans., 2000, 2, 1193—1198
[9]	Karki S. B., Treemaneekam V., KaufmanM. J., J. Pharm. Sci., 2000, 89, 1518—1524
[10]	Hartung J., Schneiders N., Gottwald T., Terahedron Lett., 2007, 48, 6027—6030
[11]	Paul H., Small R. D., Scaiano J. C., J. Am. Chem. Soc., 1978, 100(14), 4520—4527
[12]	Encinas M. V., Scaiano J. C., J. Am. Chem. Soc., 1981, 103(21), 6393—6397
[13]	Russell G.A., Reactivity, Selectivity, and Polar Effects in Hydrogen Atom Transfer Reactions, Wiley,New York, 1973, 1—13
[14]	Suleman N. K., Flores J., Tanko J. M., Isin E. M., Castaqnoli N. Jr., Bioorg. Med. Chem., 2008, 16(18), 8557—8562
[15]	Tsentalovich Y. P., Kulik L. V., Gritsan N. P., Yurkovskaya A. V., J.Phys. Chem. A, 1998, 102, 7975—7980
[16]	Baciocchi E., Bietti M., Salamone M., Steenken S., J. Org. Chem., 2002, 67, 2266—2270
[17]	Roberts B. P., Chem. Soc. Rev., 1999, 28, 25—35
[18]	Finn M., Friegline R., Suleman N. K., J. Am. Chem. Soc., 2004, 126(24), 7578—7584
[19]	Wong S. K., J. Am. Chem. Soc., 1979, 101, 1235—1239
[20]	Salamone M., Giammarioli I., Bietti M., J. Org. Chem., 2011, 76(11), 4645—4651
[21]	Poleshchuk O. K., Yureva A. G., Filimonov V. D., Frenking G., Journal of Molecular Structure, 2009, 912, 67—72
[22]	Frisch M.J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A. F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Montgomery J. A., Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Rega N., Millam J. M., Klene M., Knox J. E., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Martin R. L., Morokuma K., Zakrzewski V. G., Voth G. A., Salvador P., Dannenberg J. J., Dapprich S., Daniels A. D., Farkas O., Foresman J. B., Ortiz J. V., Cioslowski J., Fox D. J., Gaussian 09, Gaussian Inc., Wallingford CT, 2009
[23]	Lee C., Yang W., Parr R. G., Phys. Rev. B, 1988, 37, 785—789
[24]	Becke A. D., J. Chem. Phys., 1993, 98, 5648—5652
[25]	Yanai T., Tew D. P., Handy N. C., Chem. Phys. Lett., 2004, 393, 51—56
[26]	Ditchfield R., Hehre W. J., Pople J. A., J. Chem. Phys., 1971, 54, 724—728
[27]	Francl M. M., Pietro W. J., Hehre W. J., Binkley J. S., DeFrees D. J., Pople J. A., Gordon M. S., J. Chem. Phys., 1982, 77, 3654—3665
[28]	Miertus S., Scrocco E., Tomasi J., Chem. Phys., 1981, 55, 117—129
[29]	Scalmani G., Frisch M. J., J. Chem. Phys., 2010, 132, 114—110
[30]	Tao J. Y., Mu W. H., Chass G. A., Tang T. H., Fang D. C., Int. J. Quantum Chem., 2013, 113, 975—984
[31]	Zhao Y., Truhlar D. G., J. Chem. Phys., 2006, 125, 194101-1—194101-5
[32]	Chai J. D., Head-Gordon M., J. Chem. Phys., 2008, 128, 084106-1—084106-15
[33]	McLean A. D., Chandler G. S., J. Chem. Phys., 1980, 72, 5639—5648
[34]	Raghavachari K., Binkley J. S., Seeger R., Pople J. A., J. Chem. Phys., 1980, 72, 650—654
[35]	Fang D.C., Thermo Program, Beijing Normal University,Beijing, 2013
[36]	Trouton F., Philosophical Magazine, 1884, 18, 54—57
[37]	Atkins P., Physical Chemistry, Oxford University Press, London, 1978
[38]	Liang Y., Liu S., Xia Y., Li Y., Yu Z. X., Chem. Eur. J., 2008, 14, 4361—4373
[39]	Lin S. H., Lau K. H., Volk L., Richardson W., Eyring H., Proc. Natl. Acad. Sci. USA, 1972, 69, 2778—2782
[40]	Volk L., Richardson W., Lau K.H., Hall M., Lin S.H., J. Chem. Ed., 1977, 54, 95—97

Species	Reaction	CAM-B3LYP^a		CAM-B3LYP^b		M062x^a		wB97x^a		Expt.^c
Species	Reaction	ΔG^≠(g)^d/ (kJ·mol^-1)	ΔG^≠(l)^e/ (kJ·mol^-1)	ΔG^≠(g) / (kJ·mol^-1)	ΔG^≠(l)/ (kJ·mol^-1)		ΔG^≠(g)/ (kJ·mol^-1)	ΔG^≠(l)/ (kJ·mol^-1)	ΔG^≠(g)/ (kJ·mol^-1)	ΔG^≠(l)/ (kJ·mol^-1)
Amines	1+2a	51.0	23.0	57.3	28.4	43.1	15.1	48.5	20.5	29.7
	1+2b	54.4	26.3	61.1	31.8	48.1	19.7	53.9	25.5	31.4
	1+2c	64.0	35.1	63.6	35.1	56.5	28.0	65.7	37.2	32.6
	1+2d	55.6	27.6	66.9	38.5	53.1	24.7	54.4	26.8	27.6
	1+2e	45.6	18.4	51.4	23.8	43.5	16.3	47.3	20.5	27.6
	1+2f	65.7	36.8	65.6	36.4	57.7	28.9	64.4	36.4	33.0
	1+2g	70.7	43.1	68.6	40.6	63.6	36.8	72.8	45.6	33.9
	1+2h	51.4	24.3	53.1	24.7	48.5	20.1	53.9	27.2	27.2
Hydrocarbons	1+2i	67.7	38.9	76.1	47.7	54.8	26.3	64.4	35.5	36.8
	1+2j	66.5	37.6	69.0	39.7	59.0	30.1	68.2	38.9	35.5
	1+2k	63.6	34.7	63.1	33.9	57.7	29.3	65.2	36.8	36.0
	1+2l	70.3	40.6	68.6	39.3	63.6	35.1	69.4	40.6	39.3
	1+2m	77.8	49.8	74.9	46.4	74.0	46.0	78.2	50.2	43.1
	1+2n	72.8	44.3	71.5	42.2	68.2	39.7	74.9	46.4	39.3
	1+2o	83.2	55.6	82.8	55.2	75.7	48.5	85.3	57.7	46.8
Alcohols	1+2p	50.2	20.9	58.1	27.6	42.2	13.0	48.5	18.8	33.9
	1+2q	61.1	34.3	61.5	34.3	61.5	35.1	64.4	37.6	46.0
Ethers	1+2r	45.6	17.1	48.9	20.1	45.2	16.3	47.3	19.2	33.5
	1+2s	53.1	23.8	53.9	25.1	49.3	21.3	53.5	25.5	33.9
	1+2t	63.6	36.8	62.7	35.5	56.4	30.1	65.7	39.3	44.3
	1+2u	67.3	39.3	68.6	40.1	63.1	35.1	69.4	42.2	44.7

Species	Reaction	CAM-B3LYP^a		CAM-B3LYP^b		M062x^a		wB97x^a		Expt.^c
Species	Reaction	ΔG^≠(g)^d/ (kJ·mol^-1)	ΔG^≠(l)^e/ (kJ·mol^-1)	ΔG^≠(g) / (kJ·mol^-1)	ΔG^≠(l)/ (kJ·mol^-1)		ΔG^≠(g)/ (kJ·mol^-1)	ΔG^≠(l)/ (kJ·mol^-1)	ΔG^≠(g)/ (kJ·mol^-1)	ΔG^≠(l)/ (kJ·mol^-1)
Amines	1+2a	51.0	23.0	57.3	28.4	43.1	15.1	48.5	20.5	29.7
	1+2b	54.4	26.3	61.1	31.8	48.1	19.7	53.9	25.5	31.4
	1+2c	64.0	35.1	63.6	35.1	56.5	28.0	65.7	37.2	32.6
	1+2d	55.6	27.6	66.9	38.5	53.1	24.7	54.4	26.8	27.6
	1+2e	45.6	18.4	51.4	23.8	43.5	16.3	47.3	20.5	27.6
	1+2f	65.7	36.8	65.6	36.4	57.7	28.9	64.4	36.4	33.0
	1+2g	70.7	43.1	68.6	40.6	63.6	36.8	72.8	45.6	33.9
	1+2h	51.4	24.3	53.1	24.7	48.5	20.1	53.9	27.2	27.2
Hydrocarbons	1+2i	67.7	38.9	76.1	47.7	54.8	26.3	64.4	35.5	36.8
	1+2j	66.5	37.6	69.0	39.7	59.0	30.1	68.2	38.9	35.5
	1+2k	63.6	34.7	63.1	33.9	57.7	29.3	65.2	36.8	36.0
	1+2l	70.3	40.6	68.6	39.3	63.6	35.1	69.4	40.6	39.3
	1+2m	77.8	49.8	74.9	46.4	74.0	46.0	78.2	50.2	43.1
	1+2n	72.8	44.3	71.5	42.2	68.2	39.7	74.9	46.4	39.3
	1+2o	83.2	55.6	82.8	55.2	75.7	48.5	85.3	57.7	46.8
Alcohols	1+2p	50.2	20.9	58.1	27.6	42.2	13.0	48.5	18.8	33.9
	1+2q	61.1	34.3	61.5	34.3	61.5	35.1	64.4	37.6	46.0
Ethers	1+2r	45.6	17.1	48.9	20.1	45.2	16.3	47.3	19.2	33.5
	1+2s	53.1	23.8	53.9	25.1	49.3	21.3	53.5	25.5	33.9
	1+2t	63.6	36.8	62.7	35.5	56.4	30.1	65.7	39.3	44.3
	1+2u	67.3	39.3	68.6	40.1	63.1	35.1	69.4	42.2	44.7

Species	Reaction	k/(L·mol^-1·s^-1)
Species	Reaction	CAM-B3LYP	M062x	wB97x	Expt.^[18]
Amines	1+2a	6.1×10⁸	1.4×10¹⁰	1.5×10⁹	4.2×10⁷
	1+2b	1.5×10⁸	2.1×10⁹	2.2×10⁸	1.9×10⁷
	1+2c	4.2×10⁶	7.5×10⁷	1.8×10⁶	1.2×10⁷
	1+2d	9.3×10⁷	2.7×10⁸	1.2×10⁸	8.9×10⁷
	1+2e	3.9×10⁹	8.9×10⁹	1.6×10⁹	9.8×10⁷
	1+2f	2.2×10⁶	5.6×10⁷	2.8×10⁶	1.0×10⁷
	1+2g	1.8×10⁵	2.2×10⁶	6.2×10⁴	7.3×10⁶
	1+2h	3.8×10⁸	1.8×10⁹	1.1×10⁸	1.0×10⁸
Hydrocarbons	1+2i	9.2×10⁵	1.5×10⁸	3.6×10⁶	2.1×10⁶
	1+2j	1.5×10⁶	3.3×10⁷	1.0×10⁶	3.4×10⁶
	1+2k	5.3×10⁶	4.8×10⁷	2.2×10⁶	3.2×10⁶
	1+2l	4.6×10⁵	4.3×10⁶	4.8×10⁵	8.1×10⁵
	1+2m	1.1×10⁴	5.6×10⁴	9.3×10³	1.9×10⁵
	1+2n	1.1×10⁵	6.8×10⁵	4.5×10⁴	8.6×10⁵
	1+2o	1.2×10³	2.0×10⁴	5.0×10²	4.0×10⁴
Alcohols	1+2p	1.4×10⁹	3.2×10¹⁰	3.2×10⁹	6.9×10⁶
	1+2q	6.5×10⁶	4.6×10⁶	1.5×10⁶	5.3×10⁴
Ethers	1+2r	6.1×10⁹	8.2×10⁹	2.7×10⁹	7.9×10⁶
	1+2s	4.0×10⁸	1.1×10⁹	2.2×10⁸	7.4×10⁶
	1+2t	2.2×10⁶	3.3×10⁷	8.7×10⁵	1.1×10⁵
	1+2u	7.9×10⁵	4.2×10⁶	2.7×10⁵	9.5×10⁴

Species	Reaction	k/(L·mol^-1·s^-1)
Species	Reaction	CAM-B3LYP	M062x	wB97x	Expt.^[18]
Amines	1+2a	6.1×10⁸	1.4×10¹⁰	1.5×10⁹	4.2×10⁷
	1+2b	1.5×10⁸	2.1×10⁹	2.2×10⁸	1.9×10⁷
	1+2c	4.2×10⁶	7.5×10⁷	1.8×10⁶	1.2×10⁷
	1+2d	9.3×10⁷	2.7×10⁸	1.2×10⁸	8.9×10⁷
	1+2e	3.9×10⁹	8.9×10⁹	1.6×10⁹	9.8×10⁷
	1+2f	2.2×10⁶	5.6×10⁷	2.8×10⁶	1.0×10⁷
	1+2g	1.8×10⁵	2.2×10⁶	6.2×10⁴	7.3×10⁶
	1+2h	3.8×10⁸	1.8×10⁹	1.1×10⁸	1.0×10⁸
Hydrocarbons	1+2i	9.2×10⁵	1.5×10⁸	3.6×10⁶	2.1×10⁶
	1+2j	1.5×10⁶	3.3×10⁷	1.0×10⁶	3.4×10⁶
	1+2k	5.3×10⁶	4.8×10⁷	2.2×10⁶	3.2×10⁶
	1+2l	4.6×10⁵	4.3×10⁶	4.8×10⁵	8.1×10⁵
	1+2m	1.1×10⁴	5.6×10⁴	9.3×10³	1.9×10⁵
	1+2n	1.1×10⁵	6.8×10⁵	4.5×10⁴	8.6×10⁵
	1+2o	1.2×10³	2.0×10⁴	5.0×10²	4.0×10⁴
Alcohols	1+2p	1.4×10⁹	3.2×10¹⁰	3.2×10⁹	6.9×10⁶
	1+2q	6.5×10⁶	4.6×10⁶	1.5×10⁶	5.3×10⁴
Ethers	1+2r	6.1×10⁹	8.2×10⁹	2.7×10⁹	7.9×10⁶
	1+2s	4.0×10⁸	1.1×10⁹	2.2×10⁸	7.4×10⁶
	1+2t	2.2×10⁶	3.3×10⁷	8.7×10⁵	1.1×10⁵
	1+2u	7.9×10⁵	4.2×10⁶	2.7×10⁵	9.5×10⁴