期刊信息

  • 刊名： 河北师范大学学报（自然科学版）Journal of Hebei Normal University (Natural Science)
  • 主办： 河北师范大学
  • ISSN： 1000-5854
  • CN： 13-1061/N
  • 中国科技核心期刊
  • 中国期刊方阵入选期刊
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  • 河北省优秀科技期刊

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含P3H3的π-hole磷键作用及取代效应的理论研究

  • 河北师范大学 化学与材料科学学院, 化学国家级实验教学示范中心, 河北 石家庄 050024
  • DOI： 10.13763/j.cnki.jhebnu.nse.2017.06.009

Theoretical Study on the Properties of π-hole Pnicogen Bonds Containing P3H3 and Their Substituent Effects

摘要/Abstract

摘要：

采用量子化学计算方法，在MP2/aug-cc-pVDZ理论水平上对P3H3…NCX（X=H，F，Cl，Br，CN，CF3，OH，CH3，NH2，OCH3） π-hole磷键作用的性质以及取代基的影响进行了理论研究，分析了复合物的稳定结构、相互作用的强度、电子给体和电子受体间的轨道作用及电子密度拓扑性质等.研究表明，P3H3与NCX间的π-hole磷键作用为闭壳层非共价相互作用：色散和静电作用占主导地位，极化作用较小.NCX中不同取代基对氮原子上的静电势产生较大影响，进而改变了π-hole磷键作用的强度：较强的吸电子基（CN，CF3，F）减弱了π-hole磷键作用强度，给电子基（OH，CH3，OCH3，NH2）增加了相互作用的强度.复合物P3H3…NCOH中由于存在很强的LP（P）→BD*（O—H）的轨道作用，分子间相互作用强度明显增加.

Abstract：

The properties and effect of substitution on the strength of π-hole pnicogen bonds in the P3H3…NCX(X= H,F,Cl,Br,CN,CF3,OH,CH3,NH2,OCH3) complexes were investigated by quantum chemical calculations at the MP2/aug-cc-pVDZ level,include the geometries,interaction energies,orbital interactions,and electron densities.The results indicate that the π-hole pnicogen bonds belong to the typical closed-shell noncovalent interactions.Moreover,dispersion and electrostatic forces play dominant roles,while the polarization force is small.Examination of the electrostatic potentials of NCY monomers indicates that the substituents have large influence upon the most negative electrostatic potential on the surface of the interacting nitrogen and thus modulate these π-hole interactions.The replacement of hydrogen atom of HCN by the strong electron-withdrawing groups (CN,CF3,and F) leads to the interaction energys decrease.On the antrary,the replacement of hydrogen atom by the electron-donating groups (OH,CH3,OCH3,and NH2) increases the strength of in teraction energy.A far greater enhancement of the interaction in the P3H3…NCOH complex arises from the strong LP(P)→BD*(O-H) orbital interaction.

关键词

关键词： π-hole磷键作用 ; 取代效应 ; 电子密度拓扑分析 ; 能量分解分析
Key words： π-hole pnicogen-bonded interaction ; substituent effect ; topological analysis of electron density ; energy decomposition analysis

参考文献 36

  • [1] NAGY P I.Competing Intramolecular vs Intermolecular Hydrogen Bonds in Solution[J].Int J Mol Sci,2014,15(11):19562-19633.doi:10.3390/ijms151119562
  • [2] LEGON A C.The Halogen Bond:An Interim Perspective[J].Phys Chem Chem Phys,2010,12(28):7736-7747. doi:10.1039/C002129F
  • [3] CLARK T,HENNEMANN M,MURRAY J S,et al.Halogen Bonding:The σ-hole[J].J Mol Model,2007,13(2):291-296.doi:10.1007/s00894-006-0130-2
  • [4] GRABOWSKI S J.π-hole Bonds:Boron and Aluminum Lewis Acid Centers[J].Chem Phys Chem,2015,16(7):1470-1479.doi:10.1002/cphc.201402876
  • [5] ESRAFILI M D,MOHAMMADIAN-SABET F,SOLIMANNEJAD M.A Theoretical Evidence for Mutual Influence Between S…N(C) and Hydrogen/Lithium/Halogen Bonds:Competition and Interplay Between π-hole and σ-hole Interactions[J].Struct Chem,2014,25(4):1197-1205.doi:10.1007/s11224-014-0392-8
  • [6] BAUZA A,MOOIBROEK T J,FRONTERA A.Directionality of π-holes in Nitro Compounds[J].Chem Commun,2015,51(8):1491-1493.doi:10.1039/c4cc09132a
  • [7] GUO X,CAO L,LI Q,et al.Competition Between π-hole Interaction and Hydrogen Bond in the Complexes of F2XO (X=C and Si) and HCN[J].J Mol Model,2014,20(11):2493-2499.doi:10.1007/s00894-014-2493-0
  • [8] ALKORTA I,ELGUERO J,DEL-BENE J E.Pnicogen Bonded Complexes of PO2X (X=F,Cl) with Nitrogen Bases[J].J Phys Chem A,2013,117(40):10497-10503.doi:10.1021/jp407097e
  • [9] AZOFRA L M,ALKORTA I,SCHEINER S.Noncovalent Interactions in Dimers and Trimers of SO3 and CO[J].Theor Chem Acc,2014,133(12):1586-1594.doi:10.1007/s00214-014-1586-2
  • [10] POLITZER P,MURRAY J S.Halogen Bonding:An Interim Discussion.[J].Chem Phys Chem,2013,14(2):278-294.doi:10.1002/cphc.201200799
  • [11] MURRAY J S,LANE P,CLARK T,et al.σ-holes,π-holes and Electrostatically-driven Interactions[J].J Mol Model,2012,18(2):541-548.doi:10.1007/s00894-011-1089-1
  • [12] ZAHN S,FRANK R,HEY-HAWKINS E,et al.Pnicogen Bonds:A New Molecular Linker?[J].Chem-Eur J,2011,17(22):6034-6038.doi:10.1002/chem.201002146
  • [13] SOLIMANNEJAD M,GHARABAGHI M,SCHEINER S.SH…N and SH…P Blue-shifting H-bonds and N…P Interactions in Complexes Pairing HSN with Amines and Phosphines[J].J Chem Phys,2011,134(2):024312-024316.doi:10.1063/1.3523580
  • [14] SCHEINER S.A New Noncovalent Force:Comparison of P…N Interaction with Hydrogen and Halogen Bonds[J].J Chem Phys,2011,134(9):094315-094319.doi:10.1063/1.3562209
  • [15] DEL-BENE J E,ALKORTA I,ELGUERO J.Characterizing Complexes with Pnicogen Bonds Involving sp2 Hybridized Phosphorus Atoms:(H2C=PX)2 with X=F,Cl,OH,CN,NC,CCH,H,CH3,and BH2[J].J Phys Chem A,2013,117(31):6893-6903.doi:10.1021/jp4063109
  • [16] DEL-BENE J E,ALKORTA I,ELGUERO J,et al.Lone-pair Hole on P:P…N Pnicogen Bonds Assisted by Halogen Bonds.[J].J Phys Chem A,2017,121(6):1362-1370.doi:10.1021/acs.jpca.6b12553
  • [17] PECINA A,LEPSIK M,HNYK D,et al.Chalcogen and Pnicogen Bonds in Complexes of Neutral Icosahedral and Bicapped Square-antiprismatic Heteroboranes.[J].J Phys Chem A,2015,119(8):1388-1395.doi:10.1021/jp511101n
  • [18] LIU C,ZENG Y,LI X,et al.A Comprehensive Analysis of P…π Pnicogen Bonds:Substitution Effects and Comparison with Br…π Halogen Bonds[J].J Mol Model,2015,21(6):143-155.doi:10.1007/s00894-015-2697-y
  • [19] 王月红,李晓艳,曾艳丽.PO2X…PX3/PH2X(X=F,Cl,Br,CH3,NH2)复合物中π-hole磷键作用的电子密度拓扑分析[J].物理化学学报,2016,32(3):671-682.doi:10.3866/PKU.WHXB201512293
  • [20] WEI Y,LI Q,LI W,et al.Influence of the Protonation of Pyridine Nitrogen on Pnicogen Bonding:Competition and Cooperativity[J].Phys Chem Chem Phys,2016,18(16):11348-11356.doi:10.1039/C6CP00551A
  • [21] FRISCH M,TRUCKS G,SCHLEGEL H B,et al.Gaussian 09,Revision A 02[M].Wallingford:Gaussian Inc,2009.
  • [22] BOYS S F,BERNARDI F D.The Calculation of Small Molecular Interactions by the Differences of Separate Total Energies:Some Procedures with Reduced Errors[J].Mol Phys,1970,19(4):553-566.doi:10.1080/00268977000101561
  • [23] LU T,CHEN F.Multiwfn:A Multifunctional Wavefunctional Analyzer[J].J Comput Chem,2012,33(5):580-592.doi:10.1002/jcc.22885
  • [24] HUMPHREY W,DALKE A,SCHULTEN K.VMD:Visual Molecular Dynamics[J].J Mol Graph,1996,14(1):33-38.doi:10.1016/0263-7855(96)00018-5
  • [25] BULAT F A,TORO-LABBLE A,BRINCK T,et al.Quantitative Analysis of Molecular Surfaces:Areas,Volumes,Electrostatic Potentials and Average Local Ionization Energies[J].J Mol Model,2010,16(11):1679-1691.doi:10.1007/s00894-010-0692-x
  • [26] KEITH T A.AIMAll(Version 15.09.27),TK Gristmill Software[M/OL].USA:Overland Park KS,2017.http://aim.tkgristmill.com/references.html.
  • [27] MICHAEL W,SCHMIDT M,KIM K,et al.General Atomic and Molecular Electronic Structure System[J].J Comput Chem,1993,14(11):1347-1363.doi:10.1002/jcc.540141112
  • [28] MURRAY J S,RILEY K E,POLITZER P,et al.Directional Weak Intermolecular Interactions:σ-hole Bonding[J].Aust J Chem,2010,63(12):1598-1607.doi:10.1071/CH10259
  • [29] LANG T,LI X,MENG L,et al.The Cooperatitivity Between the σ-hole and π-hole Interactions in the ClO…XONO2/XONO…NH3 (X=Cl,Br,I) Complexes[J].Struct Chem,2015,26(1):213-221.doi:10.1007/s11224-014-0486-3
  • [30] NGUYEN M T,DRANSFELD A,LANDUYT L,et al.Calculated Properties and Ring-chain Rearrangements of Triphosphirane (P3H3)[J].Eur J Inorg Chem,2000,2000(1):103-112.doi:10.1002/(SICI)1099-0682(200001)2000.1
  • [31] REED A E,CURTISS L A,WEINHOLD F.Intermolecular Interactions from a Natural Bond Orbital,Donor-acceptor Viewpoint[J].Chem Rev,1988,88(6):899-926.doi:10.1021/cr00088a005
  • [32] BADER R F W.A Quantum Theory of Molecular Structure and Its Applications[J].Chem Rev,1991,91(5):893-928.doi:10.1021/cr00005a013
  • [33] BECKE A,MATTA C F,BOYD R J.The Quantum Theory of Atoms in Molecules:From Solid State to DNA and Drug Design[M].Weinham:WILEY-VCH,2007:13356-13357.
  • [34] BONE R G A,BADER R F W.Identifying and Analyzing Intermolecular Bonding Interactions in van der Waals Molecules[J].J Phys Chem,1996,100(26):10892-10911.doi:10.1021/jp953512m
  • [35] ZENG Y,WU W,LI X,et al.Influence of the Li…π Interaction on the H/X…π Interactions in HOLi…C6H6…HOX/XOH (X=F,Cl,Br,I) Complexes[J].Chem Phys Chem,2013,14(8):1591-1600.doi:10.1002/cphc.201300075
  • [36] HOBZA P,HAVLAS Z.Blue-shifting Hydrogen Bonds[J].Chem Rev,2000,100(11):4253-4264.doi:10.1021/cr990050q

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