Thuyt FMO

Bch khoa ton th m Wikipedia Bc ti: menu, tm kim Thuyt vn o bin phn t l mt l thuyt p dng ca thuyt vn o phn t nhm m t tng tc HOMO - LUMO.

Mc lc
[n]

1 Lch s 2 Hc thuyt 3 ng dng o 3.1 Cng vng o 3.2 Phn ng chuyn v sigma o 3.3 Phn ng nhit 4 Ch thch

[sa] Lch s
Nm 1952, Ken'ichi Fukui cho ra mt mt trang vit trn t Journal of Chemical Physics (Bi bo v Ha l) vi nhan "A molecular theory of reactivity in aromatic hydrocarbons" (tm dch: "Thuyt phn ng phn t ca cc hidrocacbon thm".[1] D b cng lun thi by gi, nhng sau cng vi Roald Hoffmann, ng c trao tng gii Nobel Ha hc vi cng trnh nghin cu c ch phn ng. Cng trnh ca Hoffman tp trung to ra chui cc phn ng cn vng ha hu c nh tnh i xng vn o phn t; ng l ng tc gi "The Conservation of Orbital Symmetry" (tm dch: "S bo ton tnh i xng orbital (phn t)") vi Robert Burns Woodward, ngi tng nhn c mt gii Nobel trc khi qua i. Fukui c lp nghin cu cc tng tc thng qua cc quan st vn o bin ca phn t, v cc tc ng c th ca Vn o phn t lin kt c mc nng lng cao nht (HOMO) v Vn o phn t khng/phn lin kt c mc nng lng thp nht (LUMO) ln c ch phn ng, t dn ti tn gi sau ny ca hc thuyt l Thuyt Vn o bin phn t (gi tt: Thuyt FMO). Sau , ng dng nhng tng tc nghin cu lm r Quy tc Woodward-Hoffmann.

[sa] Hc thuyt

Fukui nhn thy xp x hiu qu cho hot phn ng, cn phi quan st cc vn o (HOMO/LUMO) ngoi cng (vn o bin). Vic thng qua ba bc quan st thuyt vn o phn t (orbital) khi hai phn t tng tc: 1. Orbital lin kt ca nhng phn t khc nhau th y nhau. 2. Phn dng in ca mt phn t ht phn m in ca phn t cn li. 3. Orbital lin kt ca mt phn t v Orbital khng lin kt ca phn t cn li (c bit l HOMO v LUMO) tng tc ln nhau gy ra lc ht. T nhng quan st ny, thuyt vn o bin phn t (FMO) n gin ha hot thnh tng tc gia HOMO v LUMO ca hai phn t khc nhau. N gip gii thch d on ca Quy tc Woodward-Hoffman dnh cho phn ng nhit cn vng, c th tm tt bng pht biu sau: "Thay i trng thi nn/cn bn ca vng l c php v tnh i xng khi tng ca (4q+2)s v (4r)a l s l" (4q+2)s l con s ch h thng electron thm, ng vng khng gian; tng t, (4r)a l con s ch h thng electron khng thm, khc vng khng gian. C th nhn ra rng khi tng ca cc h trn l th phn ng c php xy ra v mt nhit hc.[2]

[sa] ng dng
[sa] Cng vng
Xem thm: Phn ng Diels-Alder Phn ng cng vng l phn ng ng thi to ra t nht hai lin kt mi, v trong chuyn binh hai hay nhiu phn t mch h thnh vng.[3] Trng thi chuyn ca nhng phn ng ny lin quan c th n cc electron ca phn t chuyn ng trn vng (gi kn) cho ra phn ng cn vng. Nhng phi ng ny c th c d on nh vo quy tc Woodward-Hoffmann v do c xp x bng thuyt FMO. Phn ng Diels-Alder gia hai phn t anhydrid maleic v cyclopentadiene c php xy ra theo quy tc Woodward-Hoffmann bi c su electron dch chuyn trong cng mt vng khng gian v khng c electron no chuyn vng. Dn ti, tng ca mt (4q+2)s v khng (4r)a l l, c ngha phn ng c php v mt nhit hc. Ngoi ra, thuyt FMO cn i xa hn trong vn d on chn lc lp th, mt kha cnh khng c Woodward & Hoffmann ni ti. V c mt h [4+2], n gin ta xt phi ng ca butadien v eten. HOMO ca butadien v LUMO ca tilen u phn i xng (i xng khi quay), nn phn ng c php.*

V mt chn lc lp th ca phn ng gia anhidrid maleic v cyclopentadien, sn phm endo c u tin, cho ta li gii thch ti u khi dng thuyt FMO. Anhidrid maleic c mang nhiu nhm ht electron, lm cho n thiu in t v tm kim phn ng vi nhng phn t di do electron, tun theo phn ng Diels-Alder mu. Do , phn ng ca HOMOcyclopentadien v LUMOanhidrid maleic c php din tin. Bt lun, sn phm exo bn hn v mt nhit ng lc hc, nhng vi cc tng tc orbital (khng lin kt) th cp, nng lng trng thi chuyn endo c gim xung v gip y nhanh tc hnh thnh nn endo c u tin v mt ng hc phn t. V c lin kt s cp nn sn phm exo vn c hnh thnh, nhng chm hn s hnh thnh ca sn phm chnh, endo.[2]

Lu : Khi LUMO v HOMO ca eten v butadien u i xng, th phn ng vn c php. Nhng khi nim ny lin quan n "s o ln nhu cu electron Diels-Alder."

[sa] Phn ng chuyn v sigma

A sigmatropic rearrangement is a reaction in which a sigma bond moves across a conjugated pi system with a concomitant shift in the pi bonds. The shift in the sigma bond may be antarafacial or suprafacial. In the example of a [1,5] shift in pentadiene, if there is a suprafacial shift, there is 6 e- moving suprafacially and none moving antarafacially, implying this reaction is allowed by the Woodward-Hoffmann rules. For an antarafacial shift, the reaction is not allowed. These results can be predicted with FMO theory by observing the interaction between the HOMO and LUMO of the species. To use FMO theory, the reaction should be considered as two separate ideas: (1) whether or not the reaction is allowed, and (2) which mechanism the reaction proceeds though. In the case of a [1,5] shift on pentadiene, the HOMO of the sigma bond (i.e. a constructive bond) and the LUMO of butadiene on the remaining 4 carbons is observed. Assuming the reaction happens suprafacially, the shift results with the HOMO of butadiene on the 4 carbons that are not involved in the sigma bond of the product. Since the pi system changed from the LUMO to the HOMO, this reaction is allowed (though it would not be allowed if the pi system went from LUMO to LUMO). To explain why the reaction happens suprafacially, first notice that the terminal orbitals are in the same phase. For there to be a constructive sigma bond formed after the shift, the

reaction would have to be suprafacial. If the species shifted antarafacially then it would form an antibonding orbital and there would not be a constructive sigma shift. It is worth noting that in propene the shift would have to be antarafacial, but since the molecule is very small that twist is not possible and the reaction is not allowed.

[sa] Phn ng nhit

An electrocyclic reaction is a percyclic reaction involving the net loss of a pi bond and creation of a sigma bond with formation of a ring. This reaction proceeds through either a conrotatory or disrotatory mechanism. In the conrotatory ring opening of cyclobutene, there are 2 electrons moving suprafacially (on the pi bond) and 2 moving antarafacially (on the sigma bond). This means there is one 4q+2 suprafacial system and no 4r antarafacial system; thus the conrotatory process is thermally allowed by the Woodward-Hoffmann rules. The HOMO of the sigma bond (i.e. a constructive bond) and the LUMO of the pi bond are important in the FMO theory consideration. If the ring opening uses a conrotatory process then the reaction results with the HOMO of butadiene. As in the previous examples the pi system moves from a LUMO species to a HOMO species, meaning this reaction is allowed.
[2]

Gin nng lng orbital t hp

Lin kt ho hc l mt kin thc rt c bn i vi anh em dn ho, th nhng, vic phc ho cho ng gin nng lng orbital t hp t hai orbital nguyn t hnh thnh lin kt qu thc ko n gin cht no. Hng ng thng 10 ny l thng sinh nht, thi ua vit bi cht lng ng gp cho chemvn, mnh s gip cc bn c ci nhn c th v su sc hn v vn gin nng lng cc orbital t hp hnh thnh lin kt.

Trc tin, ta s i vo kho st loi lin kt n gin nht, homonuclear bond, vi i din n gin nht ca ho hc Hydrogen molecule.

a. The hydrogen molecule: Tng tng rng lin kt c hnh thnh bng cch mang hai nguyn t t v cc tin n khong cch c th to lin kt. Khi cc nguyn t tin n khong cch lin kt, xut hin hai cch thc to lin kt gia chng. Th nht, nu cc orbital c cng du (cng phase), mt electron gia hai nguyn t s tng ln, v do in tch m ca cc electrons s ht hai in tch dng ca hai ht nhn. Kt qu lm gim nng lng ca ton h thng. Cch th hai, khi cc orbital to lin kt ngc du (ngc phase), v orbital t hp to thnh gi l antibonding, nu c electron trong orbital ny th s c mt rt nh, bi v hm sng ang thay i du gia hai ht nhn. Cng lp lun nh trn, do mt electron gia hai ht nhn thp, dn n s y nhau quyt lit gia hai ht nhn. Nu ta mun c electron trong orbital ny v gi cho hai ht nhn khong cch gn nhau hp l (khong cch lin kt), nng lng ca h thng s tng ln ng k.

Hnh 1: Gin cc orbital t hp ca hydrogen Nhn vo hnh trn, ta c th bin lun mt s im sau, nng lng ca h thng theo l thuyt tnh ton s b s c lm bn hai ln E , bi v c hai electron c in vo bonding orbital. Th nhng, theo kin th i cng, hai electron th nht phi ngc spin th mi sng chung mt orbital, th hai gia chng vn c mt tng tc y nhau v bn cht vn cng du in tch. Chnh v vy, thc t nng lng E . Mt bi ton thc nghim ng dng m hnh ny, chnh l gii thch v sao c phn t hydrogen H2 m ko c phn t He2. s nh hn E*

Tip theo, ta s so snh cc gin ca C-C sigma bond (trong ethane) vi C-O sigma bond (trong ethanol).

b. C-C vs C-O:

V lin kt C-C sigma bond th ni chung ko khc g my v mt cch thc to lin kt so vi hydrogen bond, nn mnh s dn ra hnh v:

Hnh 2: C-C sigma bond M hnh lin kt C-O sigma bond l i din in hnh cho heteronuclear bond. O l nguyn t c m in cao hn Carbon, do vy nng lng ca orbital nguyn t ca O s thp hn C. Tnh i xng trong s t hp mt i, dn n h s ng gp ca cc nguyn t trn t orbital t hp l khc nhau, v oxygen atom ng gp mt electron cao hn. Hay ni cch khc, h s ng gp cao hn Oxygen trong s to thnh bonding orbital, v ngc li antibonding orbital, orbital nguyn t ca carbon s c h s ng gp ln hn.

Hnh 3: C-O sigma bond. Khi h s ng gp gia hai nguyn t cho mt orbital t hp ko bng nhau, s xen ph ca small lobe vi larger lobe s ko lm gim nng lng ca bonding molecular orbital bng s xen ph ca hai orbital nguyn t c cng lobe size. Trong cc v d trn th ta thy 2Eo (fig 3) < 2E (fig 2).

Mt im ng lu y, ta phi cn thn khi nh gi mnh yu ca lin kt khi da vo gim ca bonding orbital. Chng hn nh C-C sigma bond vi C-O sigma bond c nng lng tng ng 83 kcals/mole v 85.5 kcals/mole. Gii thch rt n gin, v trong lin kt C-O, ch mt phn ng gp lm cho lin kt bn cht chnh l Eo pure covalent bonding, phn cn li l tng tc tnh in xut hin gia mt electron cao tp trung trn Oxygen vi ht nhn carbon. Chng ta thng gi m hnh lin kt ny l phn cc (polarize) hay c tnh ion.

c. T gin nng lng ti hot tnh c s: Theo lp lun trn, ta thy C-O l mt lin kt mnh, rt kh ct lin kt

C-O thnh cp radicals, nhng i vi C-C th li n gin hn. iu ny c th d dng nhn ra vi hai con s 83 (C-C) v 85.5 (C-O) trn. T d kin thc nghim trn, ta s lm r rng cc mc nng lng trong gin t hp nh sau:

Nng lng lin kt Eo chnh l nng lng bn ho ca nguyn t Oxygen khi tham gia to lin kt, Ec cng tng t chnh l nng lng bn ho ca nguyn t Carbon khi tham gia lin kt. Nh vy, vic homolysis C-O sigma bond chnh l a mt electron v li Oxygen (1 x Eo) v mt electron v li carbon (1 x Ec). Vy tng nng lng homolysis lien kt C-O sigma bond chnh l Ec + Eo. Lp lun tng t ta c nng lng ti thiu homolysis C-C sigma bond s l 2 x E .

T d kin thc nghim nu trn, ta c th predict: Ec + Eo > 2E

Ngoi ra, cng vi l gii tng t, t thc nghim heterolysis C-O sigma bond d hn C-C bond, ta a ra c tng quan gia cc mc nng lng nh sau: 2Eo < 2E .

Phn ng nhit v quang ha (pericyclic reaction)

Th T, 01/02/2012, 08:38 SA | Lt xem: 358 Hu ht cc phn ng hu c xy ra theo c ch phn cc theo kiu mt tc nhn nucleophin cho 2e vi mt tc nhn electrophin hnh thnh lin kt mi. Phn khc li phn ng theo kiu gc t do, mi cht phn ng cho 1e hnh thnh lin kt mi. V hin nay hu ht cc phn ng theo hai kiu ny c hiu bit mt cch tng tn. I. Gii thiu Mt loi th 3 na ca phn ng hu c l phn ng pericyclic (ta s gi l phn ng peri ha) l phn ng khng h xy ra theo hai hng trn m l mt qa trnh ng b xy ra theo mt trng thi chuyn tip vng (phn ng mt giai on). Phn ng ny c 3 loi: phn ng vng ha electron, phn ng cng vng (nghin cu k phn ng Diels-Alder) v phn ng chuyn v Sigma. II. Quy tc c bn ca phn ng peri ha: Quy tc Woodward - Hoffmann 1. Obitan phn t trong h lin hp pi Da vo thuyt obitan phn t (MO) th cc obitan p trong nguyn t cacbon lai ha sp2 trong mt polien lin hp to thnh mt h thng cc obitan pi c nng lng ph thuc vo s nt m chng c gia cc ht nhn. Nhng h thng c obitan vi s nt b s c mc nng lng b hn gi l cc MO lin kt. Ngc li l MO phn lin kt. Ta d dng nhn thy iu ny trong th d sau: (ng chm chm ch mt phng nt). Xt 1,3 butadien.