摘要:

J. CHEM. SOC. DALTON TRANS. 1985 873Organoruthenium(ii) Complexes formed by Insertion Reactions of Some VinylCompounds and Conjugated Dienes into a Hydrido-Ruthenium BondKatsuma Hiraki," Naoyuki Ochi, Yoko Sasada, Hideki Hayashida, Yoshio FuChita, andShunichiro YamanakaDepartment of Industrial Chemistry, Faculty of Engineering, Nagasaki University, Bunk yo -machi, Nagasaki852, JapanThe hydridoruthenium(1i) complex [RuCI(CO)H (PPh,),] (1 ) reacted easily with methyl acrylateand N,N-dimethylacrylamide to give the corresponding insertion products, [Ru{CH,CH,C(O) -OMe}CI(CO)(PPh,),] (2a) and [Ru{CH,CH,C(0)NMe,}Cl(C0)(PPh3),] (3), respectively.Similarly, complex (1 ) reacted with 2-vinylpyridine and 5-ethyl-2-vinylpyridine to afford theC1,N-chelating organoruthenium(ii) complexes, [ Ru(CH,CH,(C,H,N)}CI(CO) (PPh,),] (4a) and[Ru{CH,CH,(C,H,EtN)}Cl(CO) (PPh,),] ( 5 ) , respectively.Complexes (2a) and (4a) reacted withLiBr-H,O to give the analogous bromo-complexes. The conjugated dienes, penta-l,3-diene,isoprene, and methyl sorbate were treated with (1) to yield the q3-allylic ruthenium(i1) complexes,[Ru{q3-R1C(H)C(R2)CHR3}CI(CO)(PPh3),] [(6) R' = R3 = Me, R2 = H; (7) R' = R2 = Me, R3 = H;(8) R' = Et, R2 = H, R3 = CO,Me], respectively. On the basis of 'H and l3C-{'H} n.m.r. data, it hasbeen concluded that the two PPh, ligands in (2)-(5) are located trans to each other, whereasthose in (6)-(8) are cis.I II tI 1Insertion reactions of olefins into hydrido-ruthenium bonds arethought to be a necessary step in catalytic hydrogenations,' iso-meri~ations,'*~ hydrodimerization,4 and polymerization withruthenium complexes.It has been reported that [RuH,(PPh,),]or [RuH,(PPh,),] react with some olefinic compounds toproduce monohydrido-,6-s q3-allyl-,8 or 1-5-q-cyclo-octa-dienyl-ruthenium(@ complexes and olefin-co-ordinated ruth-enium@) c o m p l e x e ~ , ~ ~ ~ depending on the substituents. Al-though the product pattern seemed fairly complicated, thereactions involve the insertion of the olefin into the H-Ru bondof the starting complexes, accompanied by subsequent inter-ligand hydrogen transfers.'*T Moreover, [Ru(CH,=CHPh),-(PPh,),] also reacts with linear alkenes and cyclohexene '' toafford various ruthenium-(0) and -@I) complexes, whereas thereaction between [ Ru(C6H,PPh,-o)H(CH3CN)(PPh3),] andpropene gave [RuH(q '-C3H ,)(CH3CN)(PPh3),]. ' ' Bruce andco-workers l 3 found that [Ru(qS-C,H,)H(PPh,),l reacted withdisubstituted acetylenes and a highly electron-deficient olefin,(CF,),C=C(CN),, to afford insertion products.It has also beenreported that hydrido-complexes of zirc~nium,'~ molyb-d e n ~ r n , ' ~ rhodium,I6 iridium,17 and platinum lS react witholefinic compounds to give insertion products and it is wellestablished that transition-metal hydrides add to linearconjugated dienes with the formation of o- or q3-allyliccomplexes.'It was of interest to investigate the reactivity of [RuCl(CO)-H(PPh,),] (1) 'O towards olefinic compounds in comparisonwith those of [RUH,(PP~,),]~-~ or [RUH,(PP~,),J.~ It hasbeen reported that (1) reacts with various heterocumulenes 21-23and 2-acylpyridines 24 to give insertion products.Recently,we reported the preparation and co-ordination behaviour of[{ Ru(MeCHCN)C1(CO)(PPh3)z}z], which was formed by theinsertion reaction of acrylonitrile into (l)." In this paper, wereport the preparation and characterization of organoruth-enium(I1) complexes obtained by the insertion reactions of othervinyl compounds (methyl acrylate, N,N-dimet hylacrylamide,and 2-vinylpyridines) and several conjugated dienes into the-t Another mechanism, which involves reductive elimination and insome cases oxidative addition, has been p r ~ p o s e d . ~ . ~ . 'H-RU bond of (1). A preliminary letter of this study has beenpublished previously.26ExperimentalGeneral Procedures and Materials.-Melting points and i.r.and 'H n.m.r.spectra were obtained according to the liter-a t ~ r e ; ' ~ I3C n.m.r. spectra were run on a JEOL model-FX-90Qspectrometer. All preparative operations were performed in astream of dry nitrogen.The starting complex (1) was prepared according to theliterature method.'* 2-Vinylpyridine and 5-ethyl-2-vinyl-pyridine were distilled under pressure (0.73 x lo4 Pa) andstored. Solvents were dried and distilled by the usual methods.Other reagents were commercial samples, and were usedwithout further purification.Reaction of (1) with Methyl Acrylate.-A tetrahydrofuran(thf) suspension (50 cm3) of (1) (0.52 mmol) and methyl acrylate(2.1 mmol) was stirred at room temperature for 24 h.Thereaction mixture was filtered and concentrated to ca. 10 cm3under reduced pressure. The resulting solution was diluted withhexane to give a greenish grey solid, [Ru(CH,CH,C(O)-OMe ) C1( CO)( PPh ,) '3 (2a).Halogen Metathesis of(2a).-An acetone suspension (15 cm3)of (2a) (0.4 mmol), PPh, (0.4 mmol), and LiBr*H,O (3.1 mmol)was stirred at room temperature for 24 h, and filtered. The re-sulting precipitates were collected and washed with methanol-water (1 : 1) and diethyl ether to afford a pale yellow powder,[ RU{CH,CH,C(O)OM~}B~(CO)(PP~~)~] (Zb).Reaction of (1) with N,N-Dimethylacry1amide.-Complex (1)(0.42 mmol) was treated with N,N-dimethylacrylamide (2.1mmol) in thf (50 cm3) at room temperature.After stirring for 1 dthe reaction mixture became yellow, and then began graduallyto deposit a white precipitate. The precipitate was collectedand washed with hexane to afford [ ku(CH,CH,C(b)NMe2}-CI(CO)(PPh 3) z 1 (3)874 J. CHEM. SOC. DALTON TRANS. 19850C0CPh3P//##f( i i ) \( 6 ) ( R ’ = R 3 = M e , R2 = H IR3\Y( 2 a ) ( Y = OMe)( 3 Y = NMe2)0 \ CR DCH2( 7 ) ( R ’ = R 2 =Me, R3 = H I( 8 ) ( R’ = E t , R2 = H , R3 =C02Me)( 4 a ) ( R = H 1( 5 ) ( R = E t )\OMe( 2 b )0C( ivlBr -4- - - ---PPh3/ ff __t Ru I /f/ I /Ph3P-----t-- CH2\UCH2Scheme. (i) Methyl acrylate for (2a), N,N-dimethylacrylamide for (3); (ii) 2-vinylpyridine for (4a), 5-ethyl-2-vinylpyridine for (5); (iii) penta- 1,3-diene,isoprene, or methyl sorbate for (6), (7), or (8), respectively; (iv) LiBr*H,OReactions of( 1) with 2- Vinylpyridines.-A thf suspension (50cm3) of (1) (0.50 mmol) and 2-vinylpyridine (0.75 mmol) wasstirred at room temperature for 22 h.The resulting solution wasconcentrated (to ca. 25 cm3) under reduced pressure and dilutedwith hexane. A greenish grey solid precipitated, which waswashed with hexane to afford [Ru{CH,CH,(C,H,N)}Cl(CO)-(pPh3)21(4a).Similarly, (1) reacted with 5-ethyl-2-vinylpyridine for 10 hto give a greenish grey solid, [Ru{CH,CH,(C,H,EtN)}Cl-(CO)(PPh3) 21 (5).Halogen Metathesis of(4a).-An acetone suspension (15 cm3)of (4a) (0.3 mmol) and LiBr*H,O (2.4 mmol) was stirred at roomtemperature for 38.5 h, and filtered.The resulting precipitatewas collected and washed with methanol-water (1:l) anddiethyl ether to yield a white powder, [Ru{CH2CH2(C5H4N)}-Br(CO)(PPh3)2] (4)).Reactions of (1) with Conjugated Dienes.-A thf suspension(40 cm3) of (1) (0.37 mmol) and penta-1,3-diene (a cis and transmixture; 2.0 mmol) was stirred at room temperature for 3 d toproduce a yellow solution. The solution was concentrated underreduced pressure to ca. 10 cm3 and diluted with hexane to give agreenish yellow solid, [Ru(q3-MeC3H3Me)Cl(CO)(PPh,),l(6).Similarly, (1) reacted with isoprene and methyl sorbate(methyl hexa-2,4-dienoate) at room temperature to afforda greenish yellow solid, [Ru{q3-MeC(H)C(Me)CH,)CI(CO)-(PPh3)2] (7), and a yellow solid [Ru(q3-EtC3H3C02Me)C1-(CO)(PPh,),] (8), respectively.Results and DiscussionPreparations and General Properties.-The hydridoruth-enium(I1) complex (1) reacted smoothly with methyl acrylate,N,N-dimethylacrylamide, 2-vinylpyridine, and 5-ethyl-2-vinyl-pyridine in thf at room temperature to give the 2-substituted-ethyl ruthenium(1r) complexes [Ru(CH2CH2C(0)OMe}CI-(3), and [Ru{CH2CH2(CSH,RN))cl(CO)(PPh,),l [R = H (4a)or Et (5)], respectively (Scheme).When (I) was treated similarlywith conjugated dienes, i.e. penta- 1,3-diene, isoprene, andmethyl sorbate, the q 3-allylic ruthenium(I1) complexes[Ru(q3-MeC3H3Me)C1(CO)(PPh3)J (6), [Ru{q3-MeC(H)C-(Me)CH,)Cl(CO)(PPh,),] (7), and [Ru(q3-EtC3H3-CO,Me)Cl(CO)(PPh,),] (8) were formed, respectively. Com-plexes (2a) and (4a) underwent halogen metathesis byLiBr-H20 in acetone at room temperature to afford thecorresponding bromo-complexes. However, (3) and (6) did notgive pure bromo-substituted products.The yields and elementalanalyses of complexes (2)-(8) are summarized in Table 1.The i.r. spectra of (2)--(8) lacked the v(Ru-H) band near 2 OOOcm-’, observed in the starting complex (1). They showed onestrong band in the range 1887-1 940 cm-’, assignable to aterminal metal-bonded carbonyl group (Table 2), and threestrong bands near 1 090, 1 430, and 1 480 cm-’, attributable toPPh, ligands. These data, the elemental analyses, and the n.m.r.data (see later) indicate that complexes (2)--(8) are the insertionproducts of vinyl compounds or conjugated dienes into theH-Ru bond of (1).This is in sharp contrast to (q4-cyclo-octa-1,5-diene)- or (q4-buta-1,3-diene)-hydridoruthenium(~~) com-plexes, in which the diene component remains x-co-ordinatedwithout inserting into the H-Ru bond, the hydride remainingi n t a ~ t . ~ ~ - ~Complexes (2)--(8) are considerably stable in the solid statein air and fairly stable in thf under a nitrogen stream. Theconductivities of (2a), (3), (4a), and (6) were less than 4 S cm2mol-’ in acetone (0.5 x lC3 mol ~ l m - ~ ) , implying that thesecomplexes are of a non-ionic character.II(CO)(PPh 3) 21 [ Ru { CH 2CH2C(O)NMe 2} CI(CO)(PPh 3) 2J. CHEM. soc. DALTON TRANS. 1985 875Table 1. Yields and elemental analyses of the complexesYield(%I88576957521767M.p.*("C)146-147155-1652-2071 70221-229170176-177Found (calc.) (%)C H NfA\63.0 (63.45) 4.95 (4.8)60.4 (60.45) 4.55 (4.55)63.65 (63.9) 5.1 (5.1) 1.85 (1.75)65.9 (66.45) 5.0 (4.8) 1.55 (1.75)63.45 (62.95) 4.5 (4.55) 1.65 (1.65)66.6 (67.1) 5.1 (5.15) 1.75 (1.7)66.45 (66.55) 5.2 (5.15)(7) [Ru{q3-MeC(H)C(Me)CH,)CI(CO)(PPh3),] 83 214 66.45 (66.55) 5.25 (5.15)(8) [Ru(q3-EtC,H,C0, Me)CI(CO)(PPh,),] 32 94-96 64.4 (64.75) 5.2 (5.05)With decomposition.Table 2.Selected i.r. and 'H n.m.r. data'H N.m.r.6~~ I 3I.r."/cm-' RuCH,CH, moiety Allylic moietyA - r AI f >Complex v(C=O) v(C=O) RuCH, RuCH,CH, 'J(HH) H',, HZ ,J(HH) CH, CHZ1895I 8951 8941 88819001 8871918190819401640 1.25 (br t) 1.95 (t)1640 1.35 (t) 1.98 (t)I 592 1.27 (br t) 1.80 (t)- 1.65 (br t) 2.58 (t)- 1.75 (t) 2.64 (br t)- 1.66 (br t) 2.60 (t)- - -- - 1 698- 576--- 666- 3.22 (m)- 2.72 (m)3.29 (d)B- 1.96 (c)*--2.97 (s) -2.93 (s) -- 2.32 (s) -- -- --2.42 (s)- - - -- - - -0.92 (t)' 1.86 (q)c - -4.66 (t) 9 1.09 (t)' -- 1.01 (t)f - -- 1.94 (s)5.56 (t) 8 0.88 (t)' 1.35 (c)'3.03 (s)-a In KBr disc.6 value from SiMe,; br = broad, c = complex; m = multiplet, q = quartet, s = singlet, t = triplet; J values in Hz; in CDCl,, exceptfor (6). Aromatic protons are not included. ' 3J(HH) = 9 Hz. 'H n.m.r. in CD,CI,. 'J(HH) = ,J(PH) = 7 Hz. ,J(HH) = ,J(PH) = 6 Hz.,J(PH) = 6 Hz. Ir Another proton signal was not distinguished. ,J(HH) = 6 Hz.CompZexes(2) and(3).-The i.r.spectra of (2a) and (2b) exhibita strong band at 1 640 cm-', which is lower than v ( M ) for afree ester carbonyl group. It is well known that v(C--O) for anester group decreases on co-ordination to a metal, owing to thedecrease of the carboxyl double-bond order.7-' 3932*33 There-fore, it is certain that the ester carbonyl group in (2a) and (2b) isco-ordinated to the ruthenium atom. The 'H n.m.r. spectra ofthe two complexes showed a triplet near 6 1.95 [2 H,RuCH,CH,, 3J(HH) = 7 Hz for (2b)l and a broad triplet near6 1.30 (2 H, RuCH,) (Table 2). This implies that methyl acrylatehas been inserted into the H-Ru bond of (1) to form a 2-(methoxycarbony1)ethyl moiety, which serves as a five-membered C',O-chelating ligand in a similar fashion to 2-(alkoxycarbony1)vinyl m ~ i e t i e s .~ . ' ~ . ~ ~ . ~ ~ The far4.r. spectrumof (2a) also showed a band at 250 cm-' and a shoulder near 265cm-', which were assignable to Cl-Ru bonds by comparisonwith the spectrum of (2b). Furthermore, the molecular weight of(2a) was 712 (calc. 776.2), which clearly indicates that (2a) ismononuclear. On the basis of these discussions, (2a) is ascribedto a non-ionic and mononuclear structure with octahedral co-ordination, [ Ru{ CH,CH,C(O)OMe} CI(CO)(PPh,),].The "C-{ 'H) n.m.r. resonances for the 2-(methoxycarbony1)-ethyl moiety of (2a) are very simple (Table 3), showing that (2a)consists of only one isomer, in spite of many possible isomerspostulated for octahedral ruthenium(1r) complexes containingone bidentate ligand.The "C-( 'H) n.m.r.spectrum of (2a) showed two triplets at 64.3 ['J(CP) = 6.1 Hz] and207.5 ['J(CP) = 17.3 Hz] ascribable tothe ruthenium-bonded methylene carbon and carbonyl carbon,respectively. Their relatively small coupling constants confirmthat these two carbons are situated at cis positions to the twoequivalent PPh, ligands. The ester carbonyl carbon resonates asa singlet at 6 186.9, implying that the carbonyl oxygen is also co-ordinated to the ruthenium atom at a cis position to the PPh,ligands. The phenyl carbons of the PPh, ligands appeared asonly one set of signals at 6 132.9 (t, C'), 134.4 (t, o-C), 128.0 (t,rn-C), and 129.5 (s, p-C). Splitting of the first three signals wasdue to virtual coupling with the two equivalent phosphorusatoms.It is noteworthy that the virtual coupling was observedfor the aromatic carbons of the arylphosphines co-ordinated tothe octahedral ruthenium complex. These data indicate that thetwo PPh, ligands are trans to each other. On the basis of thesediscussions two structures, (A) and (B), are possible for (2a), asshown in the Figure. Two ligands of high trans influence have atendency to avoid opposite sites to each other, if the stericrequirements are negligible.34 The trans influences of alkyl and876 J. CHEM. SOC. DALTON TRANS. 1985Table 3. 'H Decoupled I3C n.m.r. data"64.3 (t)'37.8 '5.7 (t)'37.77.3 (t)'37.6'13.5 (t)'42.5 '13.4 (t)'42.573.1 (d)P*4105.359.4 (d)P88.4 (d)4104.1'J(CP)6.16.7i6.76.725.624.424.46 2J(CP)207.5 (t) 17.3208.2 (t) 17.7- k208.71' -208.9 (t) 15.2202.9 J -200.1 (t) 10.0Phenyl groupRuCH,CH, or allylic I h \moiety c-0 C' 0-c m-C6 J(CP) 6 ZJ(CP) 6 JJ(CP) 6 1 653.gd 132.9 (t) 20.7' 134.4 (t) 6.lf 128.0 (t) 3.78 129.553.8' 133.2 (t) 20.2' 134.6 (t) 5.4' 128.0 (t) 4.78 129.535.6' 133.4 (t) 20.8' 134.6 (t) 6.1' 127.7 (t) 4.98 129.2- 132.7 (t) 20.2' 134.0 (t) 5.2' 127.7 (t) 5.28 128.9- 133.2 (t) 20.2' 134.0 (t) 6.1f 127.7 (t) 4.98 128.918.7 134.5 (d) 35.1 134.9 (d) 10.8 127.9 (d) 9.4 129.717.6 (d)s 134.1 (d) 40.3 134.3 (d) 11.0 127.5 (d) 9.8 129.4 (d)'51.5" 134.4 (d) 41.5 134.4 (d) 11.0 129.7 (d)'38.8In CDCI,, except for (6); singlet unless indicated, d =doublet, t = triplet.Ester C--O, 6 186.9. ' 'J(CP) + 3J(CP).'J(CP) + "J(CP). ,J(CP) + 5J(CP). Ru-CH,CH,. Ester C=O, 6 187.7. J Coupling constant could not be detected. ' Not distinguished. ' AmideM, 6 182.3. Pyridyl carbons at 6 119.3 (C'), 121.3 (C3), 133.1 (C"), 151.2 (C6), and 166.9 (C'). " Pyridyl carbons at 6 119.4 (C'), 121.6 (C3), 135.0(C4),'l 52.4 (C'), and 166.8 (C2). In CD,Cl,. C' of allylic moiety. 4C3 of allylic moiety. ' C2 of allylic moiety. "J(CP) = 7.3 Hz; methylene carbonis observed at 6 26.7. ' "J(CP) = 2.5 Hz. " Ester C=O, 6 174.9[d, 'J(CP) =2.4 Hz].At 0 "C. ' Ru-CH,CH,.0C$1 --I --- ---PPh3I0\OMe\jH2"\( A ) (2a0C/ ,Cl--t------PPh3// RuI 1 IPh3P- - -- -1- - - c\H2R DCH2 rC l//I//Ph 3P--- -1L JFigure. Possible structures for (2a), (4a), and (5)metal-bonded carbonyl groups are normally greater than thoseof C1 and an ester ~arbonyl.~~** Accordingly, structure (A) ispreferred for (2a), where the (2-methoxycarbony1)ethyl carbon* Although the trans influence of an ester carbonyl group has neverbeen reported, it is assumed to be virtually the same as acetone.(C') is located at the trans position to the chlorine atom.Thisalso indicates that rearrangement of the co-ordinating ligandstook place in the reaction from (1) to (2a). Similarrearrangements have been found as regards (4a), (5) (see later),and the other insertion products obtained from (1).21-24Complex (2b) showed very similar 'H and I3C-{ 'H) n.m.r.spectra to those of (2a) (Tables 2 and 3), indicating that simplesubstitution of the halogeno-ligand took place in the reactioncourse from (2a) to (2b) without rearrangement of the otherligands.The amide carbonyl band at 1 592 cm-' in (3) is lower thanthat for a free amide carbonyl.This is also indicative of the co-ordination of the amide carbonyl to ruthenium, since it has beenwell established that v(C=O) for an amide group lowers on metal~o-ordination.~'.~~ Both the 'H and 13C-{'H) n.m.r. spectra of(3) were very similar to those of (2a), implying that the 2-(N,N-dimethylcarbamoy1)ethyl moiety was formed by the insertion ofN,N-dimethylacrylamide into the H-Ru bond of (l), and whichacts as a five-membered C',O-chelate, in a similar fashionto the 2-(methoxycarbony1)ethyl moiety of (2a).The stereo-chemistry of (3) was also believed to be similar to that of (2a).Complexes (4) and @).-The 'H n.m.r. spectra of (4) and (5)showed two sets of methylene proton resonances near 6 1.66(broad triplet, 2 H, RuCH,) and 2.60 [triplet, 2 H, RuCH,CH,,3J(HH) = 6 Hz], showing the formation of a 2-(2-pyridyl)ethylmoiety by insertion of a 2-vinylpyridine into the H-Ru bond of(1).It is deduced in consideration of the elemental analyses, thechelate-forming ability of the 2-(2-pyridyl)ethyl moiety, and the18-electron rule that (4) and (5) involve a five-membered C',N-chelate ring from the 2-(2-pyridyl)ethyl-ruthenium moiety.Accordingly, each of (4a) and (5) can be assigned to (C) or (D) inthe Figure.As the trans influences of alkyl and metal-bondedcarbonyl groups are normally greater than those of C1 and~ y r i d i n e , ~ ~ structure (C) is preferred for (4a) and (5), by similarreasoning to that for (2a)J. CHEM. SOC. DALTON TRANS. 1985 877produced a reactive 1 -methylallyl-hydrido-intermediate, whicheasily underwent reductive elimination, followed by n-co-ordination of another molecule of the diene.8.9Complexes (6)-(8).-The 'H n.m.r. spectrum of (6) showedtwo triplets at 6 1.09 (6 H, syn-CH,, J = 7 Hz) and 4.66 [l H,allylic H2, 'J(HH) = 9 Hz] and a multiplet near 6 3.22 (2 H,allylic anti-H' and H3). The triplet at 6 1.09 is attributed tocouplings both to the neighbouring allylic H' or H3 and to thephosphorus atom trans to the allylic carbon C' or C3.The 13C-('H} n.m.r. spectrum in CD,Cl, exhibited a doublet at 6 73.1[allylic C' and C3, ,J(CP) =25.6 Hz] and two singlets at 6 18.7(2 C, CH,) and 105.3 (1 C, allylic C'). These data indicate thatthe 1,3-dimethylallylic moiety is trans to the two PPh, ligandsco-ordinated at cis positions to each other, and has asymmetrical structure. This is supported unambiguously by theobservation of only one set of phenyl carbon resonances, Table3. Accordingly, the Cl and CO ligands are trans to each other,remaining unchanged during the reaction of (1) with penta-1,3-diene, in contrast with the cases of (2)--(5). The structure of (6)is quite similar to those of [Ru(q3-allyl)C1(C0)(PPhR'R2),](R' =R2 = Me or Ph; R' = Me, R2 =Ph), derived from[RuCl,(CO),(PPhR' R2)2] and Sn(allyl)B~,.~'Complexes (7) and (8) can also be ascribed analogousstructures to that of (6), on the basis of their 'H n.m.r.spectra.*The ,C-{' H) n.m.r. data of (8) unambiguously supported theproposed structure. Moreover, (8) exhibited two sets of C', 0-C,and p-C resonances of the cis-co-ordinated PPh, ligands and ofthe allylic terminal carbons, owing to the different substituentsat the 1- and 3-carbons of the allylic moiety. It is noted that theester carbonyl carbon (6 174.9), the methyl (6 17.6), and the p-carbons of the PPh, ligands (6 129.4 and 129.7) appeared asa doublet due to coupling to the phosphorus atom.Concluding Remarks.-The carbonylhydridoruthenium(I1)complex (1) reacted with acrylonitrile and methyl acrylateto give their insertion products, [( Ru(MeCHCN)Cl(CO)-(PPh,)2}2]25 and (2a), respectively, in sharp contrast to[RuH,(PPh,),] which gave rise to polymerization of thesevinyl compound^.^ The insertion products may be regarded asstable models for active species of polymerization. Such adifference in the reaction modes is possibly attributable to thehigh reactivities of the intermediates, which are produced by theinsertions of the monomers into the H-Ru bond of [RuH,-(PPh3)4],5 in contrast to no reactivity of [(Ru(MeCHCN)-Cl(CO)(PPh,),),] 2 5 and (2a) towards the monomers(acrylonitrile and methyl acrylate).The products of insertion of vinyl monomers into the H-Rubond of (1) so far examined are of two kinds: (i) non-chelating,with a chloro-bridged binuclear structure, e.g.[ { Ru-(RCH2CHCN)C1(C0)(PPh,),),1 (R = H or CN) from acrylo-nitrile or fumaronitrile25 and (ii) a chelate, accompanied byrearrangement of the other ligands, such as (2)-(5). Type (i)may be associated with the lack of chelate-forming ability of the2-cyanoethyl group, which would be produced by the insertionof a-cyanoethylene compounds into the H-RU bond of (1).With conjugated diolefins, (1) afforded the insertionproducts, (6)--(8), without rearrangement. The lack ofrearrangement is attributed to steric effects caused by the 2-carbon atom of the n-ally1 group and its s~bstituent,~~ andpossibly to the relatively high stability of (6)-(8), owing to theelectron delocalization effect through the n-allylic system andthe n electron-withdrawing terminal carbonyl group. However,[RuH,(PPh,),] and [RuH,(PPh,),] react with buta- 1,3-dieneto give a zero-valent n-co-ordinated complex, [Ru(q4-C,H,)-(PPh,),], and butene~.~.' It seems likely that the reactionsbetween these hydrido-complexes and buta- 1,3-diene initially* It was erroneous that in ref.26, (8) was ascribed to a structure in whichthe two PPh, ligands were located at trans positions to each other. The'H n.m.r. data of (8) in ref. 26 are revised in Table 2, owing to thecorrection of calibration.AcknowledgementsThe authors are grateful to Associate Professor HideomiKoinuma, University of Tokyo, for valuable discussions of the13C n.m.r. spectra, and thank Mr.Katsuhiro Inada for themeasurements of the 13C n.m.r. spectra.References1 C. A. Tolman, 'Transition Metal Hydrides,' ed. E. L. Muetterties,Marcel-Dekker, New York, 1971, pp. 271-312 and refs. therein.2 R. A. Shunn, Inorg. Chem., 1970,9,2567.3 S. Komiya and A. Yamamoto, J. Mol. Catal., 1979, 5, 279.4 A. Misono, Y. Uchiyama, M. Hidai, I. Inomata, Y. Watanabe, and5 S. Komiya, A. Yamamoto, and S. Ikeda, Bull. Chem. SOC. Jpn., 1975,6 S . Komiya and A. Yamamoto, J. Organomet. Chem., 1975,87,333.7 S. Komiya, T. Ito, M. Cowie, A. Yamamoto, and J. A. Ibers, J. Am.8 D. J. Cole-Hamilton and G. Wilkinson, Nouu. J. Chim., 1977,1, 141.9 S. Korniya and A. Yamamoto, Bull. Chem. SOC. Jpn., 1976,49,2553.10 B. N. Chaudret, D. J. 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ISSN:1477-9226    

DOI:10.1039/DT9850000873

出版商:RSC    

年代:1985

数据来源: RSC