Theoretical Studies on Cationic Chalcogen and Pnicogen Bonds in Binary and Ternary Complexes†

doi:10.7503/cjcu20190101

Abstract

Abstract:

The cationic chalcogen bonds and pnicogen bonds in binary complexes XH₂S⁺…NCH₂P and ternary complexes NCH₂P…PyX(X=NH₂, CH₃, H, CN, F, Cl, Br) with MP2/cc-pVDZ and cc-pVTZ were investigated theoretically. The effects of cationic chalcogen and pnicogen bond length, charge density ρ and ▽²ρ at bond critical points, van der Waals’s surface penetrating distance, the second order stabilization energy and charge transfer on the complex interaction energy were discussed. The results show that cationic chalcogen bond becomes stronger when the substituting group X is an electron-withdrawing group and that pnicogen bond becomes stronger when X is electron-donating group. The possible reason of the abnormal effect of the substituting group —CN on the stability of XH₂S⁺…NCH₂P complex was investigated with the energy-decomposition method. Further, we investigated the synergistic effects of cationic chalcogen and pnicogen bonds in the H₃S⁺…NCH₂P…PyX(X=NH₂, CH₃, H, CN, F, Cl, Br) complexes, and the influences of substituting group on the stability of these ternary complexes. By comparing the second-order stabilization energy and interaction energy of the monomers in these ternary and binary complexes, it is found that cationic chalcogen bond and pnicogen bond have positive synergistic effects on enhancing the stability of these ternary complexes.

Key words: Cationic chalcogen bond, Pnicogen bond, Synergistic effect, Bond critical point

CLC Number:

O641

TrendMD:

YI Jiang, QIN Xingmei, CHEN Feiwu. Theoretical Studies on Cationic Chalcogen and Pnicogen Bonds in Binary and Ternary Complexes^†[J]. Chem. J. Chinese Universities, 2019, 40(7): 1439.

Figures/Tables 12

Fig.1 Configuration of binary complexes XH2S+…NCH2P

Table 1 Distance(RAB) between monomers in complexes, interaction energy(ΔE), the electron density(ρ) and Laplace density(▽2ρ) at the bond critical point of the binary complexes XH2S+…NCH2P*

X	ΔE_AB/(kJ·mol^-1)	R_AB/nm	ρ/a.u.	▽²ρ/a.u.
F	-161.70	0.22306	0.0586	0.1210
Cl	-116.45	0.24421	0.0378	0.1077
C≡N	-113.77	0.25719	0.0286	0.0917
Br	-104.56	0.25104	0.0331	0.0998
H	-94.27	0.26535	0.0235	0.0836
NH₂	-91.42	0.27472	0.0202	0.0717
CH₃	-79.49	0.28409	0.0171	0.0652

Table 2 van der Waals surface penetration distance(Δd) and Wiberg bond index(WBI) of binary complexes XH2S+…NCH2P

X	ΔE_AB/(kJ·mol^-1)	Δd/nm	WBI	X	ΔE_AB/(kJ·mol^-1)	Δd/nm	WBI
F	-161.70	0.16040	0.6684	H	-94.27	0.12358	0.2985
Cl	-116.45	0.14429	0.4685	NH₂	-91.42	0.11362	0.2565
C≡N	-113.77	0.13125	0.3564	CH₃	-79.49	0.10668	0.2024
Br	-104.56	0.13842	0.4163

Table 3 ADCH charge(QNCH2P) and stabilization energy(E(2)) for binary complexes XH2S+…NCH2P

X	ΔE_AB/(kJ·mol^-1)	$E LP (N) → B D * (X — S) (2)$ /(kJ·mol^-1)	$E LP (S) → B D * (N ≡ C) (2)$ /(kJ·mol^-1)	$Q NC H 2 P$ /e
F	-161.70	176.60	11.80	0.2977
Cl	-116.45	78.23	5.94	0.2148
C≡N	-113.77	45.75	3.22	0.1749
Br	-104.56	58.48	4.60	0.1915
H	-94.27	16.95	2.51	0.1496
NH₂	-91.42	13.60	1.63	0.1308
CH₃	-79.49	12.31	1.38	0.1170

Table 3 ADCH charge(QNCH2P) and stabilization energy(E(2)) for binary complexes XH2S+…NCH2P

X	ΔE_AB/(kJ·mol^-1)	$E LP (N) → B D * (X — S) (2)$ /(kJ·mol^-1)	$E LP (S) → B D * (N ≡ C) (2)$ /(kJ·mol^-1)	$Q NC H 2 P$ /e
F	-161.70	176.60	11.80	0.2977
Cl	-116.45	78.23	5.94	0.2148
C≡N	-113.77	45.75	3.22	0.1749
Br	-104.56	58.48	4.60	0.1915
H	-94.27	16.95	2.51	0.1496
NH₂	-91.42	13.60	1.63	0.1308
CH₃	-79.49	12.31	1.38	0.1170

Fig.2 Relationship among distance RAB, interaction energy and its energy components of the complexes XH2S+…NCH2P

Fig.3 Notation of different positions in pyridine of NCH2P…PyX complexes

Table 4 Interaction energy(ΔE) of the binary complex NCH2P…PyX*

X	ΔE_BC(1)/(kJ·mol^-1)	ΔE_BC(2)/(kJ·mol^-1)	ΔE_BC(3)/(kJ·mol^-1)	ΔE_BC(4)/(kJ·mol^-1)	ΔE_BC(5)/(kJ·mol^-1)
NH₂	-29.76	-31.02	-31.48	-29.80	-27.38
CH₃	-28.34	-29.59	-29.38	-29.47	-29.01
H	-28.13	-28.13	-28.13	-28.13	-28.13
F	—	-25.32	-25.83	-25.24	-24.86
Br	—	-25.12	-25.66	-25.24	-27.63
Cl	—	-25.12	-25.62	-25.28	-28.25
CN	—	-21.68	-22.56	-22.02	-24.74

Table 5 Interaction energy(ΔEBC), distance(RBC), electron density(ρ) at the critical point of the bond, Laplace density(▽2ρ) of the complex

X	ΔE_BC/(kJ·mol^-1)	R_BC/nm	ρ/a.u.	▽²ρ/a.u.
NH₂	-31.48	0.27610	0.0218	0.0520
CH₃	-29.38	0.27849	0.0209	0.0504
H	-28.13	0.27993	0.0203	0.0494
F	-25.83	0.28251	0.0193	0.0478
Br	-25.62	0.28257	0.0192	0.0477
Cl	-25.66	0.28267	0.0192	0.0476
C≡N	-22.56	0.28603	0.0180	0.0453

Fig.4 Configuration of ternary complexes H3S+…NCH2P…PyX

Table 6 Distances(RAB) between monomers in complexes H3S+…NCH2P, distances(RBC) between monomers in binary complexes NCH2P…PyX, RAB(T)and RBC(T) in ternary complexes H3S+…NCH2P…PyX, their difference ΔRAB and ΔRBC, and density difference ΔρAB and ΔρBC at the bond critical points in the binary and ternary complexes*

X	R_AB/nm	R_AB(T)/nm	ΔR_AB/nm	R_BC/nm	R_BC(T)/nm	ΔR_BC/nm	Δρ_AB/a.u.	Δρ_BC/a.u.
NH₂	0.26535	0.25528	-0.01007	0.27610	0.23557	-0.04052	0.0049	0.0267
CH₃	0.26535	0.25659	-0.00876	0.27849	0.24076	-0.03772	0.0042	0.0231
H	0.26535	0.25729	-0.00806	0.27993	0.24354	-0.03639	0.0038	0.0214
Br	0.26535	0.25807	-0.00728	0.28257	0.24697	-0.03560	0.0034	0.0196
Cl	0.26535	0.25818	-0.00717	0.28267	0.24729	-0.03538	0.0034	0.0194
F	0.26535	0.25825	-0.00710	0.28251	0.24755	-0.03496	0.0033	0.0192
CN	0.26535	0.25955	-0.00580	0.28603	0.25311	-0.03292	0.0027	0.0165

Table 7 Comparison of second-order stabilization energies(ΔE(2)) of binary complexes XH2S+…NCH2P, NCH2P…PyX and ternary complexes H3S+…NCH2P…PyX

X	$E AB (2)$ /(kJ·mol^-1)	$E AB (T) (2)$ /(kJ·mol^-1)	Δ $E AB (2)$ /(kJ·mol^-1)	E⁽²⁾ _BC/(kJ·mol^-1)	$E BC (T) (2)$ /(kJ·mol^-1)	Δ $E BC (2)$ /(kJ·mol^-1)
NH₂	16.95	25.87	8.92	39.97	147.51	107.53
CH₃	16.95	24.49	7.53	36.75	124.86	88.11
H	16.95	23.78	6.82	34.87	113.98	79.11
Br	16.95	22.98	6.03	31.60	102.09	70.49
Cl	16.95	22.85	5.90	31.56	101.26	69.69
F	16.95	22.81	5.86	31.98	100.71	68.73
CN	16.95	21.60	4.65	27.88	83.93	56.05

Table 7 Comparison of second-order stabilization energies(ΔE(2)) of binary complexes XH2S+…NCH2P, NCH2P…PyX and ternary complexes H3S+…NCH2P…PyX

X	$E AB (2)$ /(kJ·mol^-1)	$E AB (T) (2)$ /(kJ·mol^-1)	Δ $E AB (2)$ /(kJ·mol^-1)	E⁽²⁾ _BC/(kJ·mol^-1)	$E BC (T) (2)$ /(kJ·mol^-1)	Δ $E BC (2)$ /(kJ·mol^-1)
NH₂	16.95	25.87	8.92	39.97	147.51	107.53
CH₃	16.95	24.49	7.53	36.75	124.86	88.11
H	16.95	23.78	6.82	34.87	113.98	79.11
Br	16.95	22.98	6.03	31.60	102.09	70.49
Cl	16.95	22.85	5.90	31.56	101.26	69.69
F	16.95	22.81	5.86	31.98	100.71	68.73
CN	16.95	21.60	4.65	27.88	83.93	56.05

Table 8 Interaction energy(ΔE) of complexes and the cooperative energy (Ecoop) of ternary complexes H3S+…NCH2P…PyX

X	ΔE_AB/(kJ·mol^-1)	ΔE_BC/(kJ·mol^-1)	ΔE_AC(T)/(kJ·mol^-1)	ΔE_ABC/(kJ·mol^-1)	E_coop/(kJ·mol^-1)
NH₂	-94.27	-31.48	-14.32	-181.00	-40.94
CH₃	-94.27	-29.38	-11.43	-168.82	-39.43
H	-94.27	-28.13	-10.00	-162.79	-36.08
Br	-94.27	-25.62	-6.78	-153.54	-32.57
Cl	-94.27	-25.66	-6.74	-153.24	-32.27
F	-94.27	-25.83	-6.78	-153.16	-31.98
CN	-94.27	-22.56	-1.59	-139.43	-26.71

References 37

[1]	Singh S. K., Kumar S.,Das A., Phys. Chem. Chem. Phys., 2014, 16(19), 8819—8827
[2]	Desiraju G.R., Steiner T., The Weak Hydrogen Bond in Structural Chemistry and Biology, Oxford University Press, New York, 2001
[3]	Fanfrlík J., P$\dot{r}$áda A., Padělková Z., Pecina A., Machá$\dot{c}$ek J., Lepšík M., Holub J., R$\dot{u}$ží$\dot{c}$ka A., Hnyk D., Hobza P., Angew. Chem. Inter. Ed., 2014, 53(38), 10139—10142
[4]	Singh R., Premkumar T., Shin J., Geckeler K. E., Chem. Eur. J., 2010, 16(6), 1728—1743
[5]	Morokuma K., J. Chem. Phys., 1971, 55(3), 1236—1244
[6]	Etter M. C., Acc. Chem. Res., 1990, 23(4), 120—126
[7]	Zhao J., Du J., Liu S., Yang Z. Z., Zhao D. X., Liu C., Chem. J. Chinese Universities, 2016, 37(9), 1686—1693
	(赵健, 都京, 刘硕, 杨忠志, 赵东霞, 刘翠. 高等学校化学学报, 2016, 37(9), 1686—1693)
[8]	Xu Y., Liu C., Han C. J., Pan M. Y., Sun Z. Q., Han B. Y., Yang Z. Z., Chem. J. Chinese Universities, 2019, 40(2), 288—297
	(许炎, 刘翠, 韩成娟, 潘明玉, 孙照琦, 韩冰玉, 杨忠志. 高等学校化学学报, 2019, 40(2), 288—297)
[9]	Legon A. C., Angew. Chem. Int. Ed., 1999, 38(18), 2686—2714
[10]	Politzer P., Murray J. S., Clark T., Phys. Chem. Chem. Phys., 2013, 15(27), 11178—11189
[11]	Sun X.Y., Wang W. M., Ma J., Yu S. Y., Acta Chim. Sinica, 2017, 75(1), 115—118
	(孙晓阳, 王文敏, 马晶, 俞寿云. 化学学报, 2017, 75(1), 115—118)
[12]	Zhang Z., Xie W. J., Yang Y.,Sun G., Gao Y. Q., Acta Phys.-Chim. Sin., 2017, 33(3), 539—547
	(张珍, 谢文俊, 杨奕, 孙耿, 高毅勤. 物理化学学报, 2017, (3), 539—547)
[13]	Yan X. Q., Liu Q. S., Liu Y. F., Niu Q., Chem. J. Chinese Universities, 2018, 39(4), 743—748
	(阎小青, 刘秋双, 刘云凤, 牛侨. 高等学校化学学报, 2018, 39(4), 743—748)
[14]	Zhao Q., Qi B.Y., Wang B. J., Chen F. W., Acta Chim. Sinica, 2016, 74(3), 285—292
	(赵清, 齐博宇, 王宝金, 陈飞武. 化学学报, 2016, 74(3), 285—292)
[15]	Clark T., Hennemann M., Murray J. S., Politzer P., J. Mol. Model., 2007, 13(2), 291—296
[16]	Murray S.J., Lane P., Clark T., Politzer P., J. Mol. Model., 2007, 13(10), 1033—1038
[17]	Nagao Y., Hirata T., Goto S., Sano S., Kakehi A., Iizuka K., Shiro M., J. Am. Chem. Soc., 1998, 120(13), 3104—3110
[18]	Dahaoui S., Pichon-Pesme V., Howard J. A. K., Lecomte C., J. Phys. Chem. A, 1999, 103(31), 6240—6250
[19]	Iwaoka M., Takemoto S., Tomoda S., J. Am. Chem. Soc., 2002, 124(35), 10613—10620
[20]	Adhikari U., Scheiner S., J. Phys. Chem. A, 2014, 118(17), 3183—3192
[21]	Li M., Kang H.Y., Xue X. S., Cheng J. P., Acta Chim. Sinica, 2018, 76(12), 988—996
	(李曼, 康会英, 薛小松, 程津培. 化学学报, 2018, 76(12), 988—996)
[22]	Solimannejad M., Gharabaghi M., Scheiner S., J. Chem. Phys., 2011, 134(2), 024312
[23]	Scheiner S., J. Phys. Chem. A, 2011, 115(41), 11202—11209
[24]	Alkorta I., Sánchez-Sanz G., Elguero J., Del Bene J. E., J. Chem. Theory. Comput., 2012, 8(7), 2320—2327
[25]	Liu Y. Z., Li A. Y., Acta Phys.-Chim. Sin., 2015, 31(3), 435—440
	(刘玉震, 黎安勇. 物理化学学报, 2015, 31(3), 435—440)
[26]	Wang Y. H., Li X. Y., Zeng Y. L., Meng L. P.,Zhang X. Y., Acta Phys.-Chim. Sin., 2016, 32(3), 671—682
	(王月红, 李晓艳, 曾艳丽, 孟令鹏, 张雪英. 物理化学学报, 2016, 32(3), 671—682)
[27]	Li Q.Z., Li R., Liu X. F., Li W. Z., Cheng J. B., J. Phys. Chem. A, 2012, 116(10), 2547—2553
[28]	Alkorta I., Elguero J., Solimannejad M., J. Phys. Chem. A, 2014, 118(5), 947—953
[29]	Solimannejad M., Malekani M., Alkorta I., J. Phys. Chem. A, 2013, 117(26), 5551—5557
[30]	Esrafili M. D., Vakili M., Mol. Phys., 2014, 112(20), 2746—2752
[31]	Head-Gordon M., Pople J. A., Frisch M. J., Chem. Phys. Lett., 1988, 153(6), 503—506
[32]	Boys S. F., Bernardi F., Mol. Phys., 1970, 19(4), 553—566
[33]	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. Jr., Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Keith T., 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, Revision D.01, Gaussian Inc., Wallingford CT, 2009
[34]	Lu T., Chen F. W., J. Theor. Comput. Chem., 2012,11(1), 163—183
[35]	Lu T., Chen F. W., J. Phys. Chem. A, 2013, 117(14), 3100—3108
[36]	Lu T., Chen F. W., J. Comput. Chem., 2012, 33(5), 580—592
[37]	Schmidt M.W., Baldridge K. K., Boatz J. A., Elbert S. T., Gordon M. S., Jensen J. H., Koseki S., Matsunaga N., Nguyen K. A., Su S., Windus T. L., Dupuis M., Montgomery J. A., J. Comput. Chem., 1993, 14(11), 1347—1363