Journal of Organometallic Chemistry, 390 (1990) 371-378 Elsevkr !?kquoia S.A., Lausanne - Printed in The Netherlands

JOM 20796

Carbene derivatives of areneruthenium( II) complexes in one step from terminal alkynes
Dominique Devauue aud Pierre H. Dixueuf
Luboratoire de Chimie de Coordination Organique, UR4 CNRS DO4I5, Campus de Beaulieu, UniversitP de Rennes, 35042 Rennes (France)
(Received January 22nd, 1990)

Abstract The complexes [(#-arene)Ru=C(OMe)CH,R’)Cl(PR3)]PF; (R’ = Ph; arene = Me,C,H,, ‘Pr&H,, Et&H,; PR, = PMq, PPh,, P(OMe),) have been made from RuCl,(PR,)(arene) precursors by activation at room temperature of phenylacetylene in methanol containing NaPF,. The complex with R’ = nBu, arene = Me,C,H,, and PR, = PMe, is similarly formed from hex-l-yne but much more slowly, and a complex of the type [( p-cymene)Ru=C(OMe)CH,R’)Cl(PR,)I+PF,could be obtained only when the phosphine was the bulky PPh, (lob). It has been shown that the steric hindrance by both arene and phosphine ligands contributes to the stabilization of the carbeneruthenium complexes.

Iutraduction Activation of terminal alkynes by RuCl,(PR,)( $-arene) complexes has been shown to provide a catalytic and regioselective synthesis of vinylcarbamates, whereas the isoelectronic complexes RuCl(R3P),(C,H5) are inactive [l]. A study of the stoichiometric interactions of terminal alkynes with RuCl,(PR,)( $-C,M%), one of the most efficient catalyst precursors, led to the discovery of a direct route to the first arene-ruthenium-carbene complexes [(C,M%)Ru(=C(OR)CH,R’)Cl(PMe,)]+PF; [2,3]. (The only earlier such species was [(C,M%)Ru(=CH,)(Me)(PMe, )I+, which was suggested to be formed as an intermediate by hydride elimination from (C,M%)RuMq(PMe,) [4].) The formation of carbeneruthenium complexes has been shown to proceed via the vinylidene intermediates [(C,Mq)Ru(=C=CHR)Cl(PMe,)]+, which are much more easily produced and much more reactive toward nucleophiles such as alcohols [5] than the isoelectronic cations [(C,H5)(R3P),Ru]+=C=CHR [6,7]. The corresponding carbeneruthenium complexes could not be isolated from the reaction of the related (p-cymene)RuCl,(PMe,) precursor, and it was thought that
0022-328X/90/$03.50 0 1990 - Elsevier Sequoia S.A.

%P (1 a-c 2a. 1+ a b : PMe.)]+PF.)ClRu} moiety. and (ii) the stability of the complexes markedly depends on the steric influence of the ligands rather than on the electron donating ability of the {(arene)(PR.5b) (8a) Scheme (lob) I .H.3.C.5-‘Pr. the main reason.C.)(arene) complexes la (1.) and 3a (1.5 equivalent) of phenylacetylene in the presence of one equivalent of NaPF.C. 2a (1.ruthenium bond but instead a variety of other arene along with other phosphine ligands.3a.M%) bond.. in a methanol/ dichloromethane (l/l) mixture.).5-Me. c : P(OMe).4.3. : PPh. Results and discussion The RuCl. since we now report that (i) the isolation of new arene-ruthenium-carbene complexes [(arene)Ru(==C(OMe)which do not contain the stable hexamethylbenzeneCH.R’)Cl(PR. in fact.372 this could be due to the lower stability of the Ru-($-p-cymene) than of the Ru-($-C.H. were isolated (Scheme 1).(PMe. 7a (65%) and &I (73%) respectively.H.2.5-Et. This is not.) were treated with a slight excess (1. After 45 to 60 min stirring at room temperature the orange carbeneruthenium complexes 6a (75%).

70 Hz)).Cl.5-Me&H.4 Hz)) and the non-equivalence of the arene-methyl groups in 6a and the isopropyl-methyl groups in 7a. Theoretical studies have indicated that a decrease in the acidity of the terminal alkyne should disfavor the v2-alkyne-metal to #-vinylidene-metal rearrangement [8].5-Me. Comparison of the reactivities of complexes 1 shows that the presence of the less electron-releasing phosphite ligand significantly lowers the reaction rate but does not the stability of the carbene complex.2. q2-coordination of the aIkyne.32-4. Thus the rate was markedly lower for a complex containing the weak electron donating L = P(OMe). respectively (13C{‘H} NMR.) Id was recovered unchanged after 24 h in contact with phenylacetylene and no formation of the corresponding carbene complex was observed. 7a: 5. 8a: 5.) and lc (PR. Complex la reacted with an excess of hex-1-yne in a (l/l) MeOH/CH.92 (20. ligand. 6b: 323.‘I+). and addition of methanol to the electrophilic carbon of the heteroallene moiety (Ru=C=CHR) (eq.R were isolated only after a 24 h reflux of a solution of RuCl(Ph.17-4. The complex RuCl.C. The precursors RuCl.8 Hz). 7a: 325.6 Hz).Ru+=C(OMe)CH.88 (14.R (‘) It is noteworthy that these reactions occur under very mild conditions.4.80 (20.) reacted with phenylacetylene under similar conditions to give the corresponding carbene complexes 6h (70%) and 6c (72%) after 1 and 4 h.5 Hz). From 5a an unstable product was isolated at . or even the bulky PPh.)(arene) 4a (1. but complex 9a was formed very slowly. 6c: 323. which shows the non-equivalence of the Ru=C(OMe)CH. )(Ph3P).) and phenylacetylene in methanol [6. were also treated with phenylacetylene. The RuCl. rearrangement to #-vinylidene complex.4.10 o C.6 Hz)).) complexes lb (PR. and no reaction was observed for L = CO.(PMe.2. in place of the basic PMe.P).. Evidence that the ruthenium centre is chiral is provided by the ‘H NMR spectrum.15 (26.9].H.H. after 20 h of reaction at 25 o C it was isolated in 82% yield (6 ppm Ru=C: 330. Although a reaction occurred no stable product could be isolated even at .C. {Ru-Cl v -- {Ru+$ - {Ru+=C=CHR 3 .10°C. = PPh.H.60 (18.29 (11. analogues of complexes la-3a.26 (2J(PC) 20.OMe {Ru+=C.H.2 Hz).) and !ja (p-Me-C. The low rate observed for hex-1-yne is probably due to the fact that this alkyne is less acidic than phenylacetylene. but could not be char- . 6 ppm (2J(PC)).(C. mixture in the presence of NaPF.39 (12.76 (19. whereas the isoelectronic carbeneruthenium complexes (C. $a: 324.(PR.28-4.373 The complexes 6a-Sa show in 13C{ ‘H} NMR a typical low field doublet for the carbene carbon nucleus [5] (S ppm (‘J(PC)): 6a: 392.(CO)(1.65 Hz). = P(OMe). The dissociation step is favored by basic phosphines capable of stabilizing the 16 electron cationic intermediate.3. CH. 1).36 Hz)).5-Me.(L)(arene) precursors in polar solvent. The formation of carbeneruthenium complexes 6-9 can result from the initial dissociation of one Ru-Cl bond of Ru-Cl.H.)(1. methylene protons (6 ppm (‘J(AB)): 6a: 5.

89 to 1.374 Table 1 Cyclic voltammetry of RuCl.Ph)(Cl)(PMe. (0.0 Hz)) and a low field doublet in 13C{‘H} NMR (6 ppm Ru=C: 325.(PR. the complex 5b. Wleurbanne (France).2 Hz)) characteristic of the carbene carbon nucleus coupled with a 31P nucleus./P(OMe).4 (‘J(PC) 21.89 1. Me&&/PMe. AlI solvents were dried by standard methods. (lla). M&Ha Pr/PMe.2 V El/2 &CE) Complex 2a 3a 4a 59 5b iPGGH. group on the metal centre. it is likely that the stability of the carbene derivatives depends on the steric hindrance of the ligands.02 1. are quite similar to those of la and 2a.(arene)lz complexes by the procedures previously described for the preparation of RuCl.)(arene) [10.NPF.(CO)(C..(PR.(CO)(arene) were prepared from the corresponding [RuCl .49(&J acterized. Elemental analyses were performed by the CNRS analysis laboratory.(L)arene s-1 Complex la lb IC complexes in acetonitrile containing Bu. was treated with an excess of phenylacetylene.92 0.%r/PPh. the values of the potentials indicate that the stability of the [(arene)(PR. Et&HdPMe. which do not afford stable complexes.)ClRu]-Cl complexes.09 V(SCE). MGH. Electronic and steric effects of the ancillary arene and phosphine Iigands could be evoked to account for the instability of the carbene derivatives of 4a and 5s with respect to complexes 6-9. EI /2 0. however its IR and ‘H NMR spectra are consistent with the compound Ru(C(.04 ( 3J(HH) 7.98 1. M@2WPPh3 Me&H.OMe)CH. and corresponds to a Run/Run* redox system [5].03 and 1./PMe. Since complexes 4a and 5a are the least stericalIy hindered in the series. A stable carbeneruthenium complex lob (59%) was isolated after 45 min at room temperature.1 M) at 0.)(arene) was thus undertaken (Table l).94 0.96 0.H.) [14].09 t&E) Me4GH2/PMe. and ail manipulations were conducted under nitrogen by standard SchIenk techniques. their stabilities are largely controlled by the steric hindrance of both the arene and phosphine ligands. Its ‘H NMR spectrum revealed the non-equivalence of the isopropyl methyl groups (S ppm (Me&H-): 1.)(MeC~H. which is less easily oxidized than 5a but contains a phosphine bulkier than PMq. NMR spectra . The above results show that although the formation of the carbene ruthenium arene complexes requires the presence of an electron-donating PR. W&H2/C0 Id 0.00 1.)ClRu]+-carbene complexes cannot be controlled by the electronic influence of the ligands. and showed that the oxidation of all complexes containing a PR. To check this hypothesis. Xarene) and RuCl. The oxidation potentials of 4a and 5a.(PR.’Pr)+PF. group is quasi reversible. occurs at a potential of 0. Experimental General The data complexes RuCl . Assuming that the sequence of electron-releasing moieties correlates with that of the ability of the [(arene)(PR3)ClRu]+ [(arene)(PR.13] and RuCl. A cyclic voltammetry study of the precursors RuCl.


3 (Sept.75 (s. 15. C. Me-O).)]PF.).48 g).H.Me. 127.6 Hz). 1.03.39 (AB. 1. ‘tP{ ‘H} NMR (32. P.).80 MHz. Found: C.85.29.3 (s. ‘P{‘H} NMR (32. PPh. CDCl. 122. H..)..3 (s.H. .82.3 (s.-Me). 5. 5H.Me. (9a) 9a was obtained from 0. 5.: C. C22H33C1F60.47 g). as orange crystals in 82% yield (0.40 (m.134 MHz.5.51%.)(l.4. 6H.H. 134.41.-Me). 92.H.20 Hz).). C. 5. 13C {‘H} NMR (75.15 (t. 53.Cl. 39..CH.)]PF.H. 131.5-Et. 8. >(HH) 6.8 (s.9. P.04 (s. PMe. 48.CH. H. CD.134 MHz.H. (4~) 6c was obtained from 0.: C. 309 K) S ppm: 323. 68.Ph). Ph)Cl(P(OMe). IR (KBr) v cm -I: 1290 (C-O). C6Me.23-4. P. 6H.80 MHz.21%.28 (AB.H.84. CD.60...).8 (s.P2R~ calcd. PF.2 Hz).5.88 (s.7 (d.3.5. CH.. 43.).2. 128.).Me. 132..80 (d..144. 17.5-Me. 49.9 (s. 7.3. C.6 (s. H.Me. 1.Me. 121. 2H. 7.Ph. 51.C.64 (s. 860 (P-F). CDCl.). 9. as orange-yellow crystals in 72% yield (0.). CH.. Me-O)..).H.H.OP.2 Hz). 34.2.Ph)CI(PMeS)(I.). 309 K) S ppm: 7.9. Complex [Ru(=C(OMe)CH. 2...ClF. Anal.51 (d. 129.: C. P. ‘H NMR (300.ClF.).57 g (1 mmol) of complex lb as orange crystals in 70% yield (0. 59.469 MHz. 5.9. H. 9.H. 309 K) S ppm: 8. Ru=C.61.30 (AB. C.‘Pr. 17. 27. 8.Cl. CHMe.3. Ph).. 129.11 (Sept. C{‘H} NMR (75. CH.). PPh. 2J(HH) 12. Ph)Cl(PPh.Et. t3C{ t H} NMR 975.. 68. C.134 MHz.Ph. 2J(HH) 13. 59.94 (s.Me.Me. 109. 15H.62 (s. 89.07. 21.80 MHz.). 4. Ru=C. 3H.17-4.)(C. ?(PH) 11.6 (d. 4. 4.. 56. 111.2. CH.43 g (1 mmol) of complex lc.2 Hz).)]PF. 5. P(OMe).Ph. 3H. CD.2 Hz).08 (tq. 17.HtMez). CH. Ph).26 (q. P(OMe). but after 4 h of reaction.09 (s.1.4.376 Hz). 9. 128. 31P{1H} NMR 932. 2J(PC) 8.H..2. 54.49.98 (s.9. 4. C. 309 K) 6 ppm: 7. PMe. 309 K) 6 ppm: 35.7 (s. 309 K) 6 ppm: 324. 49. *J(PC) 20.35 (m.H. Found: C. 1.).33 (s. CDCl. 309 K) S ppm: 5.OP.49. 1.5-Me& H2)]PF6 (66) 6b was obtained from 0.Me.. 3H. 3. C. PF. 309 K) S ppm: 7.69. 3H.Et.).H.57 g)_ ‘H NMR (300.92 (s. 16.4 Hz). ‘H NMR (300. IR (KBr) v cm-‘: 1280 (C-O). 9H.88.6 (s.33. 9. 23.3.6 Hz).75%. IR (KBr) v cm-‘: 1290 (C-O). Found: C.84.).3 (s.).). ‘J(PC) 36.3 (s.. Found: C.). P.38 g (1 mmol) of complex la.77-3. -144. 2H. Me-O). Complex [Ru(=C(OMe)CH. CH.H. 975 (PMe. 68. 2H. 129. P(OMe).H. Ru=C.). C. ‘J(PC) 35. PF. IR (KBr) v cm-‘: 1290 (C-O). 2H.)Cl(PMe. H. H.).Ph). 2H. C. ..ClF.Ru calcd. (8a) 8a was obtained from 0. PPh. C.). 309 K) S ppm: 323. ‘J(HH) 12.7 Hz).52 (s. -145. 133. C. CH.OP.41 (sept..Cl.469 MHz. SH. Anal. 132.. C.5 (s. 5. C.134 MHz.50 g). 132. 131. 31P{1H} NMR (32. 309 K) 6 ppm: 9..29-3.Ru calcd. 5. but after 20 h of reaction. Me-O).7 (s.56 (s. 44.Cl.51 (s.73 (d.). 4. 39.Me%H.). CH.. 100. 850 (P-F). CD&l. Me-O).).-(CH.6 Hz).469 MHz.80 MHz. H. C.)(I. ‘H NMR (300. C. ?(HH) 6. P.410 g of 3a as orange crystals in 73% yield (0. P. CD.-).45 (s.33.).H. 91. CH. 129.7 (s. 870 (P-F). 309 K) S ppm: 124. P.409 (Sept. 4.H. Hz).74 (s. PMe.H. 7.3.4 Hz). $H.0 (s. CH. PMe.-).1. 5. Me-O). 2H. 6H. 9H. CD2C12.6 (d.6 Hz)..Me.1 (s.Me. 4.49. 1. 6H.15 (d.. 17. 2H. C.22 (s. 108. .14 (s.). Me-O). PMe.).6. Ph-CH. ‘J(PC) 18. 3H.0 (s. 965 (PMe.H. CD&Y.1 (s.(CH.3 (d. CH.36 (s. C. CD&&. J(PC) 26.1 (s.5. 4. Complex [Ru(=C(OMe)CH.: C.2 (s. C. 130. 111. H..2. 3. 17. 9H.). 5H. Me-O).3 (s.66 (s. CHMq). Anal. 860 (P-F). 4. 130. PF. 2J(PH) 10. 6H.Ru &cd.144.C. CH.4.48%. Complex [Ru(=C(OMe)CH.41.). Anal.).

H.. -144. MeC&. Bnaneau.10” C-O” C as a dark-yellow powder 0. P. 860 (P-F). Le Bozec for helpful discussions. 94. 5. 3H. 985 (PMe. PF.80 MHz. Angew.)(p-Me-C. 3H.50 Hz).).).91 (t. Adv.).-). Ru=C.3 (s.0 (d.0. 5H. IR (KBr) v cm-‘: 1290 (C-O).30 g (48% yield)... 5H. 21. H. 5.). lH. Chem.85 HZ). 309 K) 6 ppm: 7. ?(HH) 8. 6. Anal. C{‘H} NMR (75.ClF... 3H. H&n.88. PMq. -?(HH) 6. 13C{lH} NM R(75.87. Organomet. 32. 309 K) 6 ppm: 7.10 (d.. *J(PI-I) 10.9. 4. 309 K) 6 ppm: 325.382 g (1 mmol) of complex 5a [12] but at a temperature of . H.H. 3H.64.96 (s.58 (Sept.Ph. Me-O). 22. 850 (P-F).3 Hz). Lecolicr.2 hz). IR (KBr) v cm-‘: 1290 (C-O).‘Pr..90 (m.27 (1986) 6333.&t. 0. 129. 1. P( ‘H} NMR (32.. 17...04 (s.-‘Pr).2. 9H. PMq. Dixncufand S.34-3.).Ru calcd. *J(E) 21. PPh. 17.). C. 54.87 (s. 14.H. 4. (CH.52 (d.. References 1 (a) R Mahe..15. 5. Org.H.).13 (d.c BOZCand P. 39. GH.). 3H. GMe.Y. *J(PH) 11. 22 (1983) 46. 317 (1986) C25. Dixnaf.79 (AB. ?(HH) 7. 2.. >(HH) 6.0 Hz). CH. J.11. 6H.H4’Pr). 309 K) ‘J(PC) 38. 5. CHMe.469 MHz. CDCl. (lla) lla was obtained from 0.).-C=Ru). 33.96 (AB.44 (d. lH. 2H.4 Hz).3.9.1 (s.38 (m. Kletzin. C@e4H2). 10.71.12. S ppm: 12. CH. Organomct. (b) R Mahe.20-4.H. 4. 51. 10. Found: C.20 (d. *J(HH) 12.5 (s. 17. MeC.).0 HZ). *J(HH) 4.80 MHz.P. 15H. 6H. 1..Cl. Anal. CHMq. ‘H NMR (300. CH.). 4 (a) H.5 Hz). H. IR (KBr) v cm-‘: 1290 (C-O). Ru=C.6 (s.377 11. P. 3H. CDCl. 2.68 (m.469 MHz. C. Kletzin. Knaup. 6.75 (s..H. P. Ph).). The instability of this complex did not allow elemental analysis and the recording of 31P or 13C NMR spectra. Complex [Ru(=C(OMe)CW. C. W. 860 (P-F’). 1. 25.HiPr)]PF.: C.20 (s. Ph-CH.15 (AB. CHMe. Found: C.X-4. C. Touchardand P.H. 54.26 (d. 3 H. P.H. to MRT for a doctorate grant to D.0 Hz). Me-(CH.. Organomet. 7.. >(HH) 8. CHMe.. Ed. >(HH) 6.69. Sasaki. (lob) lob was obtained from 0.. (80 MHz.6.10-4.Chem.J.01 (s. 66.8 (s.84 (AB. ‘H NMR CD.‘Pr). 5.36 Hz). Chcm. Acknowledgement We are grateful to Dr. 134. 1. .Chcm. D. C&Me(%).3 (s. PF.). 67. H. CHMe. CH.4 (s. Lccolicr. CD.Chcm. 3(HH) 7.). Ouzzine. 309 K) 6 ppm: 35. 94. 9H. 309 K) S ppm: 330. 1. Werner.7 (s.Ph.H. Ph)Ci(PMe.73 (s. 3I-k MeC.27 (s. MeC.48 g).09 Hz.). (b) H. *J(PC) 20. P. 54 (1989) 1518. Le Bozec. CDCI. Dixneufand S. 1.).Cl.6 (s. 1. H.57 g (1 mmol) of complex 5b [12] as orange crystals in 59% yield (0. PMe.134 MHz. CHMe. (CH@). A.: C. 980 (PMe. Complex [Ru(=C(OMe)CH. 306 (1986) 227.-‘Pr)]PF.22%.. 132.3 (s. CD2Cl.5 (s.7 (s. H. PI%.2.). p-Me-qH. TetrahedronL. 4H. CH. CHMe. 17. 1.5 Hz).. Ph)Cl(PPh.9 Hz).Me..64%. 39.J. 2H. 2 K. 2H. PMe.). and to Johnson Matthey Chemicals Limited for a loan of ruthenium trichloride. 1. Werna and H.D.0 (s.Me. Paul and W. (CH.4 (Sept. L.0 Hz). ht.72. 109.3 (Sept.9 (s. 54. Dixneuf.ClF60P2Ru cakd. 107. 29 (1989) 163.0 HZ).5. Me-O).&). Eng. -144. 133.H.4 (d. ?(HH) 6.80. Me-O). 7.2 HZ). CHMe.-Me. *J(HaHb) 11. 96. 2H. 7. ‘*P{‘H} NMR (32.1. 98.8 HZ). @HH) PI%.. 2. H.Ph).)(p-Me-C.OP.46 (s. 6H.77 (s.

. Chirn... Bennett. Chem. J. Orgrmomet. Smith. 33 (1980) 1471. J. Werner and R..B.W. .C. Adv. Robertson.A. Organometallics.L. K. Commun. 6 MI. Bruce and A. 50 (1972) 3063. Helv. H.. Jr and W. J. 22 (1983) 59..A. Inorg.. Chem. 13 J. Swincer. These Universite de Rennes. Gladfelter. BNIX and A. Dalton Trans.A.M.W. Chem. 11 M. 68 (1985) 1461. Werner.I. Oumine. Zelonka and M. unpublished results. 9 M.5 K. I. J. Chem. 7 R. Tucker. Sot. 12 M.G.G. 19 (1980) 1014. Can. 14 H. J. (1989) 165.A. Matheson. Aust. Chem. Dixneuf. Hoffmann. (1974) 233. Chem. T. Swincer. Sylvestre and R. Baird.H. 174 (1979) C67.A. Chem. K. Grganomet. Le Bozec..A. 10 R. Sot. Bennett and K. 8 J. Smith and P. 3 (1984) 605. G. Acta. Chem. Bullock. Hull. 1988. Chuzine and P..