第25卷第3期濟(jì)南大學(xué)學(xué)報(bào)(自然科學(xué)版)Vol.25 No.32011年7月JOURNAL OF UNIVERSITY OF JINAN (Sci. and Tech. )Jul. 2011文章編號(hào):1671 -3559(2011)03 -0239 -04二氟鍺烯與乙烯環(huán)加成反應(yīng)的機(jī)理廉貞霞,盧秀慧.(濟(jì)南大學(xué)化學(xué)化工學(xué)院,山東濟(jì)南20022)摘要:用二階微擾和密度泛函理論研究單重態(tài)F2C=Ge:與CH環(huán)加成反應(yīng)機(jī)理,采用MP2/6 -31G*和B3LYP/6 -31C"方法計(jì)算勢(shì)能面上駐點(diǎn)的構(gòu)型參數(shù)、振動(dòng)頻率和零點(diǎn)能;利用CCSD(T)//MP2/6 -31G*和CCSD(T)//B3LYP/6 -31C*計(jì)算各構(gòu)型的能量;利用CCSD(T)//MP2得到單線態(tài)F2C=Ge:與CH環(huán)加成反應(yīng)的勢(shì)能面,在常溫常壓下,單線態(tài)F2C=Ge:與CH的環(huán)加成無勢(shì)壘放熱反應(yīng)生成三元環(huán)中間體INT,放出能量為29.5kJ .mol-'.關(guān)鍵詞:F2C=Ge:;環(huán)加成反應(yīng);二階徽擾理論;勢(shì)能面中圖分類號(hào):0621.13文獻(xiàn)標(biāo)志碼:ALaw of Cyclic Addition Between Difluorogermylene and Ethylene(School of Chemistry and Chemical Engineeing, University of Jinan ,Jinan 250022 ,China)Abstract: The law of cyelic addition between singlet difluorogermylene and ethylene has been investigated with MP2/6-31C* andB3LYP/6-31G* methods , including geometry optimization, vibration analysis and zero-point energy for the involved stationary points onthe potential energy surface. Energies for the involved configurations are calculated by CCSD( T)//MP2/6-31G* and CCSD(T)//B3LYP/6-31C* methods , respectively. On the basis of the surface energy profle oblained with CCSD(T)//MP2/6-31C* method forthe cyclic addition between singlet difluorogermylene and ethylene , it can be predicted that cyelic addition between singlet difluorog-ermylene and ethylene is a barrir-free exothermic reaction of 29. 5 kJ/ mol of a three-member ring intermediate INT.Key words :diluorogermylene ;cyclie addition;second-order perturbation theory ; potential energy surface鍺烯(R,Ge:)是一種極其活潑的活性中間究[-8] ,但是關(guān)于鹵代鍺烯的環(huán)加成反應(yīng)機(jī)理,至今體",鍺烯的反應(yīng)被認(rèn)為是合成含鍺雜環(huán)化合物和尚未見文獻(xiàn)報(bào)道,為研究鹵代鍺烯與對(duì)稱性的π鍵含鍺新鍵化合物的很有效的方法,并且鍺烯的反應(yīng)化合物的環(huán)加成反應(yīng)的反應(yīng)機(jī)理,選取單線態(tài)的也是有機(jī)鍺化學(xué)中的一個(gè)極其活躍的研究領(lǐng)F2C=Ge:與C2H,兩個(gè)分子作為研究模型,對(duì)它們域l'-5),尤其是自人們發(fā)現(xiàn)了很多有機(jī)鍺化合物具之間的環(huán)加成反應(yīng)機(jī)制作理論計(jì)算,并對(duì)反應(yīng)機(jī)理有生物活性以來,鍺烯的反應(yīng)就更成為研究的熱點(diǎn)。作了理論分析。另據(jù)Hermann等[6報(bào)道,已分離出兩種穩(wěn)定的1計(jì)算方法R,Ge:,并可用作化學(xué)氣相沉積( CVD)制備鍺膜的前軀體,因此,研究鍺烯及鍺烯反應(yīng)有著重要的理論利用Gaussian 程序, MP2/6 - 31C*[9]和和實(shí)際意義。鍺烯的環(huán)加成反應(yīng)已有初步研B3LYP/6 -31C10-1的計(jì)算方法,全參數(shù)優(yōu)化了環(huán)加收稿日期:2010-12 -03網(wǎng)絡(luò)出版時(shí)間:2011 -01 -中國(guó)煤化工基金項(xiàng)目:國(guó)家自然科學(xué)基金( 20973084)作者簡(jiǎn)介:廉貞霞( 1983 -),女,山東臨沂人,碩士生;盧秀慧(1956-),男,LYHCNMHG網(wǎng)絡(luò)出版地址:t://ww. enki. net/kcm/ deail37.1378. N. 20110118. 2204.002. html240 .濟(jì)南大學(xué)學(xué)報(bào)(自然科學(xué)版)第25卷成反應(yīng)的勢(shì)能面上的各個(gè)駐點(diǎn),全部構(gòu)型的能量也MP2/6- 31C*和B3LYP/6 - 31G"兩種水平下都進(jìn)行了CCSD(T)和零點(diǎn)能的校正，通過振動(dòng)分析F2C=Ge:與C2H在反應(yīng)的過程中形成的中間體來確認(rèn)每個(gè)平衡構(gòu)型和過渡態(tài)的構(gòu)型的真?zhèn)?通過(INT)過渡態(tài)(TS)及產(chǎn)物(P)的構(gòu)型參數(shù)非常近內(nèi)察反應(yīng)坐標(biāo)[12-13]的計(jì)算來確定過渡態(tài)屬性。似(見圖1)。圖1中R,和R2為反應(yīng)物。用這兩種理論計(jì)算2結(jié)果與分析方法所得到的:GeFz與C2H,兩分子的所發(fā)生的環(huán)計(jì)算結(jié)果表明,F2C =Ge:的基態(tài)是單線態(tài),在加成反應(yīng)的機(jī)制也很- -致。F(1)1.782. ,nF(I)(1.772)1.768(1.757).F(2)Ge (97.2)(96.8)2.844、F(2)(2.863)R，H(I)H(1).1336.. .... H(3)H(2)C(1) L.344 C(2)H(4)CI)=“(1.340)(121.9)“H(4)∠F(I)GeC(I)C(2) = 49.5(49.5)R2∠F (2)GeC(1)C(2) = -48.6(-48.4)a R,,R2b INT1.763、F(1)F(2).(1.750)/ oF(2)1.752(1.738)(1.750)121.9122.7)(123.0)Ge1.9801.897(1.991)(1.900)64.6cu))(73.0)_-..... H(3)C(1)5(64.9)1.607C(2)" " H(3)H111.452H(1)"(1.612)(1.464)H (2)∠F(1)GeC( )C(2)=693(71.4)CF(1)GeC(1)C(2)= 107.( 107.7)C F(2)GeC(I )C(2)=-69.3(-71.4)CF(2)GeC(I)C(2)=. 107.9-107.7)c TsdPMP2/6 -31G* (B3LYP/6-31C*) ; 鍵長(zhǎng):0.1 nm;鍵角: (°)圖1 F2C = Ge:和C.H4環(huán)加成反應(yīng)中各物種構(gòu)型參數(shù)和原子示意圖通過B3LYP/6 - 31G* , MP2/6 - 31G* , CCSD方法下的能量值基本相近;利用CCSD(T)//B3LYP(T)//B3LYP和CCSD(T)//MP2的計(jì)算方法所得和B3LYP計(jì)算而得到的總能量的差值很大，通過以到的各個(gè)物種的能量均列于表1。上的比較可得,用MP2/6 - 31G*和CCSD(T)//由表1可知,采取MP2/6 -31G*和B3LYP/6 -MP2/中國(guó)煤化工的差值比較小，31C*的方法計(jì)算所得到的各個(gè)物種的能量差值比因此Y片CNMHG的能量值和MP2/較大,但在CCSD(T)//MP2和CCSD(T)//B3LYP6-31C*計(jì)算所得的構(gòu)型參數(shù)作為依據(jù)來對(duì)反應(yīng)進(jìn)第3期廉貞霞,等:二氟鍺烯與乙烯環(huán)加成反龐的機(jī)理241行解釋和討論。(2) INT經(jīng)過渡態(tài)異構(gòu)化成為了P,其勢(shì)壘為圖2中列出了表1中的反應(yīng)勢(shì)能面圖,由圖2152. 8kJ●mol~'。知,反應(yīng)由兩步組成:(1)兩反應(yīng)物生成一個(gè)INT,此圖3顯示了F,C= Ge:和C2H的分子軌道對(duì)稱時(shí)為放熱反應(yīng)并且無勢(shì)壘能量是29.5kJ . mol-';性的匹配情況。表1兩種理論方法得到的物 種的總能量(E,)和相對(duì)能量(E)kJ. mol-'B3LYP/6 -31C*MP2/6 -31C*CCSD()//MP2CCSD(T)//B3LYP物種EE。E，R+R2 -6 178 522.00.0-6 172 160.0.0-6 172 302.4-6 172 304.8NT -6178551.1 - 29.1-6172193.8-33.8-6172331.9 - 29.5-6172334.2 - 29.4rs -6178398.9 123. 1-6 172048.3111. 7-6172179.1 123.3-6172182.2 122.6P-6178 456.165.9-6172 130.99.1-6172 251.2 51.2-6 172 353.950.9注:B, =Em# +Enp;B_=E, -Eu+m鍵,由于通過這種成鍵作用而生成的二氟鍺雜環(huán)丙130pTS烷的三元環(huán)構(gòu)型中存在較大的張力,故使得二氟鍺110雜環(huán)丙烷處于較高的能量狀態(tài)。90;ηs0E5之DIEt R,R1000~NT4p30F-295(CCSD(T)//MP2/6-31C* )圖2 F2C=Ge:和 CH的環(huán)加成反應(yīng)勢(shì)能面根據(jù)圖1和圖3可以分析說明該反應(yīng)機(jī)理，由對(duì)稱性匹配條件得出,當(dāng)F2C=Ge:與C2H4反應(yīng)時(shí),圈3 F2C=Ge:和 CH的分子軌道對(duì)稱性匹配因F2C=Ge:中Ge原子的4p空軌道先插人到C2H,分子中的π軌道,π電子向4P空軌道遷移,從而形由反應(yīng)的勢(shì)能面圖2可知,INT異構(gòu)為P需翻成了π-→p授受鍵,生成INT, 隨著反應(yīng)繼續(xù),由于越152.8kJ●mol~'的勢(shì)壘,P的能量比兩反應(yīng)物的FRC = Ge:在C(1)GeC(2)的平面內(nèi)發(fā)生了逆時(shí)針能量高51.2kJ●mol-', 所以在通常情況下,F2C=的旋轉(zhuǎn),[ CFGeC(1)逐漸增大(INT:95.3° ,TS:Ge:與C2H,的環(huán)加成反應(yīng)將終止于INT。即:在通121.99, P:236.59)],在INT-→TS- →+P的反應(yīng)過程常情況下,單重態(tài)二氟鍺烯與乙烯的環(huán)加成反應(yīng)將中,∠C(2)C(1)Ge和Ge-C(1)鍵長(zhǎng)逐漸變小是一個(gè)生成三元環(huán)INT的無勢(shì)壘的放熱反應(yīng)。這-(INT:79.6° ,0. 2844 nm;TS:74. 9 ,0. 198 0 nm;P:環(huán)加成反應(yīng)的情況與單重態(tài)鍺烯與乙烯的環(huán)加成反64.6° ,0. 189 7 nm);C(1) -C(2)鍵逐漸拉長(zhǎng)(乙應(yīng)')發(fā)生了質(zhì)的區(qū)別。烯:0.133 6 nm,INT:0. 134 4 nm,TS:0. 145 2 nm,P:3結(jié)論0. 1607 nm) ,使C(1) - C(2)雙鍵逐漸轉(zhuǎn)化成了單鍵,從而使INT經(jīng)TS變?yōu)榱硕N雜環(huán)丙烷。用CSD(T)//MP2方法計(jì)算得到的單線態(tài)在二氟鍺雜環(huán)丙烷中, Ge - C(2)間是因Ge原F2C=Ge;與CH,環(huán)加成反應(yīng)的勢(shì)能面,得出在常子的σ孤對(duì)電子與C(2)端的π°空軌道形成σ→溫常中國(guó)煤化工，的環(huán)加成反應(yīng)π°授受鍵而成鍵, Ge -C(1)間是因Ge原子的4p生成!YHCNMHG無勢(shì)壘的放熱反空軌道與C(1)端的π軌道形成π→p授受鍵而成應(yīng),放出熱量為29.5kJ●mol~'。242濟(jì)南大學(xué)學(xué)報(bào)(自然科學(xué)版)第25卷參考文獻(xiàn):Cheinity.1992,104(11):1489 - 1492.7] 盧秀慧,王沂軒,劉成卜.鍺婼與乙烯環(huán)加成反應(yīng)的理論研究1] BENAVIDES G M, BALASUBRAMANIAN K. 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