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nl/locate/jorganchem Journal of Organometallic Chemistry 617 – 618 (2001) 511 – 519

Neutral carbene and vinylidene cyclopentadienyl ruthenium complexes with PPh2(2-MeC6H4)
Walter Baratta a,*1, Alessandro Del Zotto a, Eberhardt Herdtweck b, Sara Vuano a, Pierluigi Rigo a,*2
b a Dipartimento di Scienze e Tecnologie Chimiche, Uni6ersita ` di Udine, Via Cotonificio 108, I -33100 Udine, Italy Anorganisch -chemisches Institut, Technische Uni6ersita ¨ t Mu ¨ nchen, Lichtenbergstrasse 4, D -85747 Garching, Germany

Received 7 August 2000; accepted 19 September 2000

Abstract The complex [RuCl(h5-C5H5){PPh2(2-MeC6H4)}2] (1), unlike the triphenylphosphine analog [RuCl(h5-C5H5)(PPh3)2], reacts under mild conditions with CO, N2CPh2 and HC CPh to give the neutral carbonyl, carbene and vinylidene derivatives [RuCl(h5-C5H5)(L){PPh2(2-MeC6H4)}] (L = CO 2, CPh2 5, C CHPh 6), respectively, via displacement of one phosphine ligand. The vinylidene complex 6 promptly reacts with benzylamine affording the aminocarbene [RuCl(h5-C5H5){ C(NHCH2Ph)CH2Ph} {PPh2(2-MeC6H4)}] (7). Moreover, the cyclometalated derivative [Ru(h5-C5H5){PPh2(2-CH2C6H4)}{PPh2(2-MeC6H4)}] (4) has been obtained from the methyl complex [RuMe(h5-C5H5){PPh2(2-MeC6H4)}2] (3) by intramolecular C – H bond cleavage and methane elimination. Complex 1, whose X-ray structure analysis is also reported, has been found to catalyze alkyne coupling reactions. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Ruthenium; Carbenes; Vinylidenes; Cyclometalation
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1. Introduction The easily accessible half-sandwich ruthenium complex [RuCl(h5-C5H5)(PPh3)2] exhibits a rich chemistry, which is an area of current active interest [1]. Its high reactivity appears to be related to the facile displacement of one of the coordinate ligands, affording neutral or cationic 16-electron unsaturated species. In polar solvents the chloride is readily exchanged with neutral ligands (L), providing a convenient entry for a variety of cationic complexes of the type [Ru(h5-C5H5)(PPh3)2(L)]+ (L = CO, RCN, PR3, etc.) [1c]. In non-polar solvents, dissociation of one PPh3 leads to the transient [RuCl(h5-C5H5)(PPh3)] complex, which can add p-acceptor ligands such as CO [2] and monodentate phosphines [3]. However, the extrusion of PPh3 to create coordinative unsaturation requires severe conditions [2], and this limits the synthetic and catalytic
*Corresponding author. E-mail: inorg@dstc.uniud.it *Corresponding author. Tel.: + 39-432-558801; fax: + 39-432558803; e-mail: pierluigi.rigo@dstc.uniud.it
2 1

applications of [RuCl(h5-C5H5)(PPh3)2]. Thus, displacement of one PPh3 and formation of neutral vinylidene complexes has not been observed in the reaction with 1-alkynes, whereas this process readily occurs in the case of [RuCl(h5-C5Me5)(PPh3)2] [4]. Werner successfully synthesized the first neutral cyclopentadienyl vinylidene complex [RuCl(h5-C5H5)( C CHCO2Me)(PPh3)], but in a stepwise process starting from the allyl derivative [Ru(h3-C3H5)(h5-C5H5)(PPh3)] [5]. By contrast, cationic complexes of general formula [Ru(h5C5H5)( C CHR)(PPh3)2]+ have been obtained by ready dissociation of the halide, especially in polar solvents [6]. Recently, we have reported that the complexes [RuCl(h5-C5H5)(PR3)2] can act as effective catalysts in a variety of reactions involving diazocompounds, such as stereoselective carbene–carbene coupling [7], cyclopropanation [8], carbene insertion into N–H and S–H bonds [9], and nitrogen ylide generation [10]. The key step of these catalytic processes is the formation of the carbene intermediate [RuCl(h5-C5H5)( CHR)(PR3)] from the 16-electron species [RuCl(h5-C5H5)(PR3)].

0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved. PII: S0022-328X(00)00675-6

67 913.99° [13]). −3) Largest difference peak and hole (e A a from [RuMe(h5-C5H5){PPh2(2-MeC6H4)}2] (3) through methane elimination. Furthermore.27 Monoclinic P 21/c (no.C5H5){ C(NHCH2Ph)CH2Ph}{PPh2(2 .0943 0.446(1) 11. 70°C. complex 1 was investigated by X-ray singlecrystal analysis. / Journal of Organometallic Chemistry 617–618 (2001) 511–519 Bulky phosphines favor the reaction as shown by the fact that [RuCl(h5-C5H5){PPh2(2-MeC6H4)}2] (1) is catalytically active below 20°C.) b (A . The facile displacement of one phosphine in complex 1 is also apparent in the reaction with diethyl maleate (DEM) which leads to the formation of complex [RuCl(h5-C5H5)(h2-DEM){PPh2(2-MeC6H4)}] [7b]. 14) 11.8].26 R1 = (.26–25. Among the few cyclopentadienylruthenium compounds bearing phosphines with a cone angle larger than that of PPh3 (145°). the signal broadens and at − 80°C the spectrum displays an AX pattern with two doublets at l = 43. whose X-ray structure is also reported. The crystallographic parameters are collected in Table 1.MeC6H4)}] (7).0327/0.) a (A . Results and discussion 2. 9 14.408 1656 0. We report herein the preparation in high yield of the new carbene and vinylidene derivatives [RuCl (h5-C5H5)( CPh2){PPh2(2-MeC6H4)}] (5) and [RuCl(h5-C5H5)( C CHPh){PPh2(2-MeC6H4)}] (6) from the easily available precursor 1.6.2 and 35. whereas an ORTEP view of 1 is shown in Fig.60. Thus. The Ru–P and Ru–Cl distances are very similar to those reported for the PPh3 analog but with a slightly smaller P–Ru–P angle (101. whereas the PPh3 analog needs heating at 60°C [7b]. The easy cleavage of one Ru–P bond in 1 prompted us to carry out a specific investigation on its properties and its ability to form isolable neutral carbene and vinylidene derivatives.238(2) 98. Although there is no significant structural difference between the PPh3 and the PPh2(2-MeC6H4) derivatives. at 20°C the 31P{1H}-NMR spectrum shows a sharp singlet at l = 37. Ruthenium organometallic compounds of this type continue to attract interest.0686/0 0. 3) V (A Z Dcalc (g cm−3) F (000) v (mm−1) q range for data collection (°) Limiting hkl indices Reflections collected Independent reflections (all data) Observed reflections (Io| (Io)) Data/restraints/parameters R1 a (Io| (Io)/all data) wR2 b GOF c Weights a /b d .606 2. The 31P-NMR spectra of 1 show that the compound has a fluxional behavior in solution on the NMR time-scale. whereas at lower CO C45H45ClOP2Ru 800. The geometry of 1 is distorted octahedral about the ruthenium center due to the severe steric interactions between the phosphines. 1 has been found to be the most reactive in several catalytic reactions [7b. Baratta et al.512 W.0453 0. but decomposes in air within a few minutes at room temperature with the formation of phosphine oxide and brown insoluble products. 1 with selected bond distances and angles. was found to catalyze the cyclotrimerization of dimethyl acetylenedicarboxylate. The two phosphorus ligands are not equivalent and one methyl group of the tolyl substituent is directed towards the chloride ligand.1. On cooling. their behavior in phosphine-substitution reactions is markedly different.01(1) 3775.936 0.P) = 35. we have recently isolated the complex [RuCl(h5-C5H5){PPh2(2-MeC6H4)}2] (1) in high yield in a one-pot reaction from ruthenium trichloride. ¸¹¹¹¹¹¹¹¹¹º The cyclometalated derivative [Ru(h5-C5H5){PPh2(2CH2C6H4)}{PPh2(2-MeC6H4)}] (4) is easily formed Table 1 Crystallographic data for 1·C2H6O Empirical formula Formula weight Crystal system Space group Unit cell parameters . 9 34 52576 6847 5118 6847/0/469 0.4 Hz. because of their potential use in stoichiometric and catalytic C – C bond forming reactions [11] and alkyne dimerization [12]. With the aim of comparing structurally the PPh3 and the PPh2(2-MeC6H4) systems.797(1) 28. −0.7(5) 4 1. It has been reported that one PPh3 ligand in [RuCl(h5-C5H5)(PPh3)2] can be replaced by CO under forcing carbonylation conditions (150 atm carbon monoxide.) c (A i (°) . 2.12° versus 103. The observed behavior is reversible and may be explained by the low temperature restricted rotation of the phenyl and tolyl rings that leads to the magnetic inequivalence of the two phosphorus atoms. Complex 6 reacts with benzylamine affording the aminocarbene [RuCl(h5 . complex 1. and 2J (P. Complex 1 is thermally stable in toluene solution under inert atmosphere even at 100°C. Structural characterization and reacti6ity of [RuCl(p 5-C5H5){PPh2(2 -MeC6H4)}2] (1) During studies directed towards the synthesis of cyclopentadienylruthenium complexes containing bulky phosphines. cyclopentadiene and PPh2(2-MeC6H4) [7b].9 and no phosphine dissociation is observed even at 100°C. 48 h) [2].

.

Fo.

−.

Fc.

.

)/ .

Fo.

2 2 2 2 1/2 wR2 = [ w (F 2 . b . o−F c ) / w (F o) ] c 2 2 1/2 GOF = [ w (F 2 .. o−F c ) /(NO−NV)] d 2 2 2 w = 1/[| 2(F 2 o)+(aP ) +bP ] with P : [max (0 or F o)+2F c ]/3.

W. Selected bond lengths [A 2.45(9). and is shifted 12 cm − 1 to lower wavenumbers compared to [RuCl(h5C5H5)(CO)(PPh3)] [14].12(2). 1. Ru–C2 omitted for clarity. C1 – Ru – P1 92. Hydrogens . Ru – P1 2. Ru – C1 2. Ru–C4 2. in agreement with the more basic character of the ortho -methylated phosphine.8. Cen: centroid of the C5H5 – ligand.167(3). Ru – P2 2. Cl–Ru–Cen 123. Ru – P1 – C21 125. ] and angles [°]: Ru – Cl 2.3271(7). Scheme 1.92(3). Ru – C3 2.3390(8).9. Ru – P2 – C51 112. The 13C{1H}-NMR spectrum of 2 in CDCl3 shows a doublet at l = 203.203(3). Thermal ellipsoids are at the 50% probability level.67(9). Ru–C5 2.0 Hz). Ru – P2 – C41 114. Ru – P2 – C61 119.18(9).20(11). the monocarbonyl derivative [RuCl(h5-C5H5)(CO){PPh2(2-MeC6H4)}] (2) was obtained quantitatively by stirring 1 under 1 atm CO at room temperature within a few minutes (Scheme 1).P) = 20.167(3). pressure (2 atm) sulfur is needed to remove the phosphine as S PPh3 [14].204(3).71(8).34(9). Ru –P1–C11 111. Ru–P1–C31 114. ORTEP representation of the molecular structure of 1 in the solid state. P1 – Ru – P2 101. Baratta et al.85(3). C1 – Ru – P2 87. .198(3). P2 – Ru – Cen 122.2.8 (2J (C. whereas the wCO appears at 1946 cm − 1. P1 – Ru–Cen 120.4372(8). By contrast. / Journal of Organometallic Chemistry 617–618 (2001) 511–519 513 Fig.

This product slowly decomposes in solution at room temperature with methane evolution and the reaction can be readily monitored by 31P{1H}-NMR.4 with a 2J (P.H) = 15.1 (part of an AXY spin system. When heated in toluene at 70°C. The most characteristic feature in the 1H-NMR spectrum of 3 is the presence of a triplet at l = 0. Preparation of carbene and 6inylidene complexes The synthesis of electrophilic carbene complexes of ruthenium still remains an area of great interest because of the manifold applications in organic synthesis for C–C carbon bond forming reactions. In both cases cyclometalation probably occurs by intramolecular C–H bond cleavage. Indeed. 2 J (C. Treatment of 1 in toluene at − 40°C with a slight excess of methylmagnesium bromide in diethyl ether gave complex 3. Complex 1 is also an excellent starting material to give neutral alkyne or vinylidene ruthenium complexes.5. The yellow complex 4 was isolated and fully characterized. Addition of a twofold molar amount of PPh3 to 1 at 50°C gives [RuCl(h5-C5H5)(PPh3)2] quantitatively. It should be mentioned that we have recently reported that complex 1 and the PPh3 analog efficiently catalyze the cyclopropanation of styrene and other electron-rich alkenes in the presence of ethyl diazoacetate. cyclometalation was not observed even when it was refluxed in toluene and in the presence of base.514 W.P) = 6. The 31P{1H}-NMR spectrum . attempts to obtain 4 by treatment of 1 with Na2CO3 in 2-propanol or CaH2 in toluene resulted in the formation of only trace amounts of the cyclometalated product. Moreover. treatment at 25°C of 1 in C6D6 with an equimolar amount of PPh3 promptly affords the mixed phosphine complex [RuCl(h5-C5H5)(PPh3){PPh2(2MeC6H4)}]. which was isolated in 81% yield and characterized by elemental analysis and NMR spectroscopy (Scheme 1). Consistent with the cyclometalated structure.6-Me2C6H3}2] stabilized by two agostic interactions [16]. starting from the methyl derivative [RuMe(h5-C5H5){PPh2(2-MeC6H4)}2] (3).82 with a 3J (H.P) = 41.P) = 15. However. We have now found that compound 1 reacts with diphenydiazomethane in toluene at 40°C affording the green carbene complex [RuCl(h5-C5H5)( CPh2){PPh2(2MeC6H4)}] (5). as result of a formal :CPh2 – :CHCH2Ph coupling.5 Hz and a doublet of doublets at 4. attributed to the Ru C carbon.1 Hz.P) = 7. In the 1H-NMR spectrum the two signals due to the Ru – CH2 methylene appear as a doublet at 4.2.0 Hz as inferred by 1 H{31P}-NMR experiments. / Journal of Organometallic Chemistry 617–618 (2001) 511–519 Moreover. For these catalytic reactions there is strong evidence that complexes of type 5 are key intermediates in the C–C coupling processes [8]. and more recently to prepare a 14-electron complex [RuCl2{PPh2(2. which was isolated as yellow powder in 78% yield (Scheme 1). selective dimerization of alkynes [12] is thought to occur via ruthenium vinylidene intermediates which are also involved in various other ruthenium catalyzed reaction of acetylenes [20]. Aryl phosphines with methyl groups in ortho position have been extensively employed to synthesize cyclometalated complexes [15]. However. which result from intramolecular C–H activation of methyl groups.8 with 2J (P. formation of 4 is favored by the more facile dissociation of one phosphine to give the coordinatively unsaturated 16-electron species [RuMe(h5-C5H5)(PR3)]. It should be noted that cyclometalation in 3 proceeds more easily than in the PPh3 analog [RuMe(h5-C5H5) ¸¹¹¹¹¹¹¹¹¹¹¹¹º ¸¹¹¹¹¹¹¹¹¹¹º 5 5 5 2 (PPh3)2] for which heating at 100°C for 6 h is necessary.7 Hz. Furthermore. Treatment of 1 in CDCl3 with an equimolar amount of internal alkynes RC CR containing electron-withdrawing groups such as R = CO2Me leads to the alkyne complex [RuCl(h5-C5H5)(h2-MeO2CC CCO2Me){PPh2(2-MeC6H4)}] which was found in equilibrium with the starting product. We can observe that a related ¸¹¹¹¹¹¹¹º cyclometalated complex [RuCl{PPh2(2-CH2C6H4)}(h6C6Me6)] was obtained by the reaction of [RuCl2{PPh2(2-MeC6H4)}(h6-C6Me6)] with Na2CO3 in 2-propanol [19]. when diphenyldiazomethane is employed as carbene source.3 Hz. as result of complete displacement of PPh2(2-MeC6H4). 3 is quantitatively converted into complex 4 within 30 min (Scheme 1). whereas the 13 C-NMR DEPT spectrum shows a singlet at l = 1.4 Hz) was attributed to the RuCH2 carbon through a 13C-NMR DEPT experiment. Therefore. whose 31P{1H}-NMR spectrum exhibits two doublets at l = 40. the cyclometalated complex [Ru(h -C H ){PPh (2CH2C6H4)}{PPh2(2-MeC6H4)}] (4) can be easily obtained according to the procedure adopted by Lehmkuhl for the synthesis of the orthometalated product [Ru(h5-C5H5){PPh2(2-C6H4)}(PPh3)] [17].2 and 59. the 13C{1H}NMR signal at l = 13.3 with a 2J (C. these values are similar to those reported for [RuCl(h5C5H5)( CPh2)(PPh3)] [11b]. The strongly downfield-shifted resonance is attributed to the P atom of the cyclometalated phosphine that is part of a five-membered chelate ring [18].3-triphenylpropene.3 Hz. 2J (C.P) = 12. 2.26 ppm with a J (H. In the case of 1. Baratta et al.P) = 34.44 ppm with a J (H.1. attributed to the Ru – CH3 methyl. induced by the generation of a vacant coordination site at the metal center. the 31P{1H}-NMR spectrum shows two doublets at l 75.P%) = 8. Complex 4 is relatively stable in solution and no phosphine displacement was observed by reaction with CO or CNtBu ligand.8 and 38. The presence of a carbene ligand in 5 was unambiguously established by the 13C{1H}-NMR spectrum which contains a typical doublet at l = 319. the reaction with styrene affords mainly 1.2 Hz.

Probably. The most characteristic feature in the 13C{1H}-NMR spectrum of 6 is the presence of a doublet at l = 345. The results here obtained for 1 can be compared with those previously reported for the 16electron derivatives [RuCl(h5-C5Me5)(L)] (L = N -heterocyclic carbene).02 for the cyclopentadienyl ring and l = 3. complex 6 is formed in low amounts along with catalytic conversion of phenylacetylene into the dimers arising from head-to-head and head-to-tail alkyne coupling.08 for the cyclopentadienyl ligand and a broad signal at 3. a catalytic cyclotrimerization occurs at room temperature with 90% conversion of the alkyne into hexamethyl benzenehexacarboxylate after 1 day [22].0 ppm with J (C.74 ppm for the vinylidene proton. Concluding remarks This study has revealed that the use of PPh2(2MeC6H4) as auxiliary ligand in cyclopentadienylruthenium complexes gives rise to a derivative related to [RuCl(h5-C5H5)(PPh3)2].4 Hz for the carbon bound to ruthenium.3 Hz for the Ru C carbon. This results from the high tendency of 1 to release one phosphine ligand to give the coordinatively unsaturated [RuCl(h5-C5H5){PPh2(2-MeC6H5)}] species which can add a variety of p-acceptor ligands. The 31P{1H}-NMR spectrum shows a signal at l = 51. which also shows a high tendency to release a phosphine ligand in solution.6 with a J (P.W.1. Also the type of alkyne seems to be important for the isolation of the vinylidene derivative. but with a remarkably higher reactivity. which has been used as phosphine scavenger for ruthenium complexes [23]. By contrast. When complex 1 (3 mol%) is added to a CDCl3 solution of dimethyl acetylenedicarboxylate. The easily accessible complex 1 is a convenient starting material for the preparation of neutral cyclopentadienylruthenium carbene and vinylidene derivatives. whereas the 1H-NMR spectrum shows a singlet at 4. Finally. The nature of the solvent seems to play a delicate role for the isolation of the vinylidene complexes. if toluene is used instead of CHCl3. the p-alkyne intermediate was not detected.P) = 16. with HC CtBu we were able to detect the corresponding vinylidene complex. in 1:10:2 molar ratio at 70° C for 5 min. which have been isolated.39 for the NH proton with two doublets at l = 4. on the basis of thermochemical studies on [RuCl(h5-ligand)(PR3)2] complexes [28]. the high steric requirements of the PPh2(2-MeC6H4) ligand are responsible for the weakening of the Ru–P bond in 1.74 for the C CH vinylidene proton. which agree well with the literature data [27]. are thought to be key intermediates in C–C bond . 3. With the latter. The formation of the aminocarbene ligand was unequivocally established by 1H and 13C-NMR spectroscopy.83 and 3. In the reaction performed without CuCl we observed a lower conver- sion into the vinylidene complex (30%) and prolonged heating of the reaction mixture led to catalytic alkyne dimerization. stoichiometric C–C coupling reactions of terminal alkynes in cyclopentadienyl ruthenium complexes have been extensively described [25]. it is well known that these species promptly react with primary amines to give aminocarbene complexes via intermolecular nucleophilic attack of the nitrogen atom [26]. and these values are close to those given by [RuCl(h5-C5Me5)( C CHPh)(PPh3)] [4a]. Thus. we observed highly efficient catalytic dimerization of terminal alkynes. treatment of a CHCl3 solution of 1 with phenylacetylene in excess at reflux affords the neutral vinylidene complex [RuCl(h5-C5H5)( C CHPh){PPh2(2-MeC6H4)}] (6). CO2Me) in CHCl3 leads to mixtures of products. Reaction of a CDCl3 solution of 1 with HC CtBu in the presence of CuCl. whereas the 13C{1H}-NMR spectrum shows a doublet at 255. The 1H-NMR spectrum of 7 exhibits a signal at l = 10. By contrast. / Journal of Organometallic Chemistry 617–618 (2001) 511–519 515 exhibits a signal at l = 45. The new ruthenium complexes 5 and 6. which can be compared with those of 6. as suggested by Nolan et al. isolated as a pale brown powder in 63% yield (Scheme 1). On the other hand. SiMe3. The systems [RuCl(h5-C5H5)(PR3)2] with bulky phosphines are currently under investigation to establish their potential in catalytic alkyne coupling reactions.C) = 20. allowing easier formation of the 16-electron complex intermediate. It should be noted that the reaction of the above-mentioned [OsCl(h5-C5H5)(PiPr3)2] with phenylacetylene initially gives [OsCl(h5-C5H5)(h2-HC CPh)(PiPr3)] which subsequently isomerizes to [OsCl(h5-C5H5)( C CHPh)(PiPr3)] [21]. whereas the 1H-NMR spectrum shows a resonance at l = 5. It should be noted that a similar p-alkyne complex [OsCl(h5-C5H5)(h2-MeCO2C CCO2Me)(PiPr3)] has been obtained by reaction of the alkyne with [OsCl(h5C5H5)(PiPr3)2] [21]. Baratta et al. Thus. we tested the reactivity of the rutheniumvinylidene 6 towards nucleophiles such as amines. whereas the 1H-NMR spectrum shows singlets at l = 5.5.89 for the diasterotopic CCH2 protons. which was isolated in 55% yield after appropriate work-up (Scheme 1). Due to the electrophilic character of the a-carbon atom in vinylidene complexes. In fact. Although the reaction of 1 with a series of terminal alkynes HC CR (R = CH2Ph. afforded almost quantitatively the complex [RuCl(h5t C5H5)( C CH Bu){PPh2(2-MeC6H4)}] as inferred by 1 H and 31P-NMR data. treatment of 6 with an equimolar amount of benzylamine at room temperature in toluene led to complex [RuCl(h5-C5H5){ C(NHCH2Ph)CH2Ph}{PPh2(2-MeC6H4)}] (7). in the formation of 6 from 1. the reaction of 1 with terminal alkynes leads to formation of neutral vinylidene derivatives.52 ppm for the methyl protons of the coordinated alkyne. with no detection of the corresponding vinylidene complexes [24].

H) = 15. RuCH3). H.0– 6. J (C.5 (s. 3. 1. 134.4 (d. 5H. 4.220 g (75%). 3H. 3H.77 (s. C5H5). whereas complex 6 is formed in the catalytic phenylacethylene dimerization. J (C. 1H.4 Hz.P) = 34. Yield: 0.P) = 2. CC H3). Yield: 151 mg (86%).0 (d. 133. Solvents were carefully dried by conventional methods and distilled under argon before use.P) = 4. J (C. C H3).P) = 10. 5H.530 mmol) dissolved in toluene (20 ml) at − 40°C.38.6 Hz. 0. for C43H38P2Ru: C.2. 13C{1H}-NMR (C6D6.82 (t. H.8 (d. J (H. It is noteworthy that in the reactions of alkynes with [RuCl(h5-C5H5)(PR3)2] systems. J (C. J (C. 128. 84.65 (s. 0. 71. the solvent was removed and pentane (5 ml) was added affording a yellow product. After filtration on alumina.23 (s.26 (s. C5H5).P) = 9. Calc. C O). Synthesis of [RuMe(p 5-C5H5){PPh2(2 -MeC6H4)}2] (3) Methylmagnesium bromide (0. Thus. IR (nujol): w (CO)=1946 cm−1. m -C6H4). J (C.P) = 12. 6H. 28H.77.7 (m.2 Hz).7 (d. Phenylacetylene. 31P{1H}NMR (C6D6. aromatic protons).4 Hz.P) = 45.4 Hz.5 Hz. 25°C): l = 75. 13C{1H}-NMR (CDCl3.304 g (78%).4 Hz. The product was filtered.0 Hz. 131. m -C6H5). Synthesis of [Ru(p 5-C5H5){PPh2(2 -CH2C6H4)}{PPh2(2 -MeC6H4)}] (4) The complex 3 (0.P) = 20. The yellow mixture was allowed to attain room temperature and stirred for 15 min. 25°C): l = 53.P) = 8.42 –6.H) = 15. 23.P) = 34.P) = 2. 5H. 58.3 Hz. 132.386 mmol) . 0. Anal. ¸¹¹¹¹¹¹¹¹¹¹¹¹º 4. o -C6H5). In conclusion.63 (m.7 Hz.345 mmol) was dissolved in 5 ml of toluene and the solution was stirred under CO (1 atm) at room temperature for 1 h. Calc. 31P{1H}-NMR (C6D6.35. C5H5). CH3).0 (d. complex 1 provides a useful alternative to the widely employed PPh3 analog in catalytic processes which occur through phosphine displacement.5 (s. / Journal of Organometallic Chemistry 617–618 (2001) 511–519 forming reactions. Synthesis of [RuCl(p 5-C5H5)(CO){PPh2(2 -MeC6H4)}] (2) The complex 1 (260 mg. H. Yield: 0. in ppm. 0.95. H. 59. J (C.0– 6.9 (d. 28H.400 g. 5.516 W. Diphenyldiazomethane (75 mg. C5H5). 3H. Anal.9 (aromatic carbons).21 ml of a 3. J (H. J (C. C Me). CH3).8 Hz. H. 0.6 (m. 1H. 4. 4. 128. RuCH2). C5H5).08 (dd.2 (d.0 Hz.5 Hz.772 mmol) were dissolved in 10 ml of toluene and the red solution was stirred at 45°C overnight.0– 124. ipso -C6H5). 4.1.3. The compounds 1 [7b] and N2CPh2 [29] were prepared according to the literature. 85. benzylamine and methylmagnesium bromide 3. IR spectra were recorded with a Nicolet Magna 550 FT spectrometer. 59. 25°C): l = 8. Anal. recrystallized from toluene–heptane and dried under reduced pressure. N) were performed by the Microanalytical Laboratory of our department. 25°C): l = 8.P) = 46.1. 130.4. 23.35.5 (t. displacement of one PR3 ligand and formation of a neutral complex have not been observed prior to this work.61.0 Hz.P) = 10. J (H. 1. J (C.2 Hz). C5H5). J (C. and to external 85% H3PO4 for 31P. aromatic protons).P) = 7. o -C6H5).300 g.1 Hz. J (C. J (C.P) = 1.77 (s.65%. 71.P) = 7. 72.8 (d. Spectroscopic data: 1H-NMR (CDCl3. The volume was reduced to 2 ml and heptane was added affording a yellow precipitate. 125. J (C. 4. J (P.2 (d.0–124. Found: C. 25°C): l = 146. 1.4 (d.9 Hz. o -C6H4). H.34.4 (d. J (P. Experimental All reactions were carried out under an argon atmosphere using standard Schlenck techniques. Elemental analyses (C.630 mmol) was added dropwise to 1 (0. 4.1 (dd. Found: C.5 (d. 5°C): l = 138. 31P{1H}-NMR (CDCl3. 0.0 M solution in diethyl ether. 14H.2 (p -C6H4 and p -C6H5).1 Hz. 13.9.90. Baratta et al. 0.0 Hz. 71. 4. 0. m -C6H5). m -C6H4).5 (aromatic carbons). aromatic protons). 4. After filtration the product was washed with heptane and dried under reduced pressure. J (C. NMR measurements were carried out using a Bruker AC 200 spectrometer.P) = 11. The solvent was eliminated and the oily product was treated with pentane (5 ml) affording a yellow precipitate. 141.0 M solution in diethyl ether were purchased from Aldrich Chemical Co. RuC H3). recrystallized from toluene–heptane and dried under reduced pressure.44 (d.P) = 10. which was filtered. 132. are relative to TMS for 1H and 13C.P) = 9. J (C. Spectroscopic data: 1H-NMR (C6D6. J (C. for C25H22ClOPRu: C.3-triphenylpropene from diphenyldiazomethane and styrene [8].P) = 10.2 (d.08 (s. 23. 5. 134.P) = 6.409 mmol) was dissolved in toluene (5 ml) and the solution was heated at 70°C for 30 min.9.29%.5 (t. CH3).5 (d. 4.0 Hz. the carbene derivative 5 has been found to be involved in the catalytic synthesis of the trisubstituted olefin 1. 2. J (H. Synthesis of [RuCl(p 5-C5H5)( CPh2) {PPh2(2 -MeC6H4)}] (5) The complex 1 (260 mg. 5. 4.02.2 Hz. RuCH2). for C44H42P2Ru: C. 25°C): l = 7. Chemical shifts. 25°C): l=46. C H3). 5.4 (d. 13C{1H}-NMR (C6D6. RuC H2).345 mmol) and diphenyldiazomethane (150 mg.6 (d. 25°C): l = 203. H. Found: C.5 – 130.9 Hz.4 Hz. J (C. Spectroscopic data: 1H-NMR (C6D6. ipso -C6H4). 83. J (C. Calc.P) = 5.41%.5 Hz.

J (H. Baratta et al.P) = 5 Hz. 31P{1H}-NMR (C6D6. 1. All hydrogen atoms were calculated in ideal positions (riding model).4 (d. 0.0 Hz. 5H. 25°C): l = 255. 1. J (C. C H3).2 Hz. C5H5). C CH ). 5. 23. 4. 19H. J (C.P) = 15. 13C{1H}-NMR (CDCl3. 4. Yield: 0. J (C.0 Hz. for C37H32ClPRu: C.5. 1H. fixed and sealed.200 g.H) = 14. aromatic protons).0 Hz.8 – 6.H) = 15. C H3). C H3).67°.33 mmol) dissolved in chloroform (20 ml). 25°C): l = 50.93 g ml − 1. SIR92.P) = 2.0 Hz. All non-hydrogen atoms of the compound 1·C2H6O were refined anisotropically. 165. 66. Calc. 67.8 (m. J (C.H) = 15. 31P{1H}-NMR (CDCl3. C5H5). Calc.43.1. 69.34 × 0. NH ). A total number of 52576 reflections were collected.2 Hz. Calc. C H2Ph). 90. decay and absorption effects. 81. J (C.2 (d. Ru C ).0 (d. H.2 (s. 4. A clear red–brown fragment (0. The unit cell parameters were obtained by 0. H.487 g (63%). aromatic protons). Synthesis of [RuCl(p 5-C5H5)( C CHPh){PPh2(2 -MeC6H4)}] (6) Phenylacetylene (1.16. 23. H.8 (aromatic carbons).2 (s. J (C. 4.001.16%. 25°C): l = 319. Anal. Found: C.P) = 4.19 (s.94.5. C5H5). All calculations were performed on a DEC 3000 AXP workstation and an Intel Pentium II PC. oscillation scan modus € = 0° to 360° with D€ = 1.42 × 0. 25°C): l = 5.5 Hz. 5H.04. Neutral atom scattering factors for all atoms and anomalous dispersion corrections for the non-hydrogen atoms were taken from International Tables for Crystallography. J (C. Synthesis of [RuCl(p 5-C5H5){ C(NHCH2Ph) CH2Ph}{PPh2(2 -MeC6H4)}] (7) Benzylamine 45 ml (d = 0. CH2C ). The solution was heated at the reflux point for 1 h and the solvent was completely removed under reduced pressure.85 (s. H. 4.75 –6. After filtration the solution was concentrated to 1 ml and heptane (4 ml) was added affording a yellow precipitate.P) = 16.2 – 125. NC H2).5 ml.26° B q B 25.3 (aromatic carbons). N.2–124.H) = 15. C5H5).7 (d. 92.P) = 2.6 (d.3 Hz. 66.2 (s. J (H. N. After filtration.10. CH2NH). 5H. 23.3 (d.8 (m. Anal. 5.W.3 Hz. 13. 118. After merging (Rint = 0. and SHELXL-97 [30].6 (aromatic carbons). including the programs PLATON. Addition of heptane (10 ml) afforded a green precipitate which was recrystallized from toluene – heptane and dried under reduced pressure.0°). The structure was solved by a combination of direct methods and difference Fourier syntheses.57 mm) was stored under perfluorinated ether. ipso -C6H5). 25°C): l = 7. transferred in a Lindemann capillary. Found: C. 24H.01. J (C. which was stirred at 55°C for 2 h and concentrated to 1 ml.P) = 20.69 (s. 142. Full-matrix least-squares refinements with 469 parame2 2 ters were carried out by minimizing w (F 2 o − F c ) with the SHELXL-97 weighting scheme and stopped at shift/ err B 0. 3H. 51.7–6. / Journal of Organometallic Chemistry 617–618 (2001) 511–519 517 was added to the resulting green solution.5 ml. 69. the product was dissolved in chloroform (20 ml) and phenylacetylene (1. 5.28. Suitable single crystals for the X-ray diffraction study were grown by cooling a concentrated solution of 1 in dichloromethane –ethanol.73 (s. Spectroscopic data: 1H-NMR (C6D6. 5. Fr951) and graphite monochromated Mo–Ka radiation (u = .412 mmol) was added to 6 (0.3 Hz. 4. X -ray structure determination for the complex 1 ·C2H6O Crystal data and details of the structure determination are presented in Table 1. 0.13 g (55%). Stoe&Chi) equipped with a rotating anode (Nonius. 32.98 g ml − 1.P) = 5. 144.9. 2.4 Hz. ). Yield: 180 mg (81%). 1H. 13C{1H}-NMR (C6D6. The solution was refluxed for 1 h and the solvent was removed under reduced pressure.5 (d. J (C. exposure time 300 s per image. Spectroscopic data: 1H-NMR (CDCl3.P) = 4. Preliminary examination and data collection were carried out on an imaging plate diffraction system (Ipds. 4. 10. 25°C): l = 44.042) a sum of 6847 independent reflections remained and were used for all calculations.7 mmol) was added to 1 (1.30. aromatic protons). 1H. 2. 4. with the STRUX-V system.26.87. 24H.93%.H) = 3. Ru C ). J (H. CH3). CH2NH).00. 142. 1. 3. 1. C5H5). J (C.30 (dt.6 (d.74 (s. 3H. H. J (H. 25°C): 345.7 mmol) was added.71073 A full-matrix least-squares refinement of 4705 reflections.3– 125. Supplementary material Crystallographic data (excluding structure factors) for the structure reported in this paper have been . Data collection were performed at 293 K (q range 2. 13. polarization. 8. 31P{1H}-NMR (C6D6. d = 0.P) = 3.83 (d.6.6 (d. 1H. 25°C): l = 7.345 mmol) dissolved in toluene (6 ml) and the solution was stirred for 30 min. C5H5). The resulting oily product was treated with 50 ml of heptane and the suspension was stirred overnight. 3H.89 (d.37 (s. Yield: 0. CH2C ).01 (dd.7. Spectroscopic data: 1H-NMR (C6D6.5 Hz. J (H. C HPh).1 Hz. for C32H28ClPRu: C. 4. 1H. 1H. The product was suspended in heptane (50 ml) and stirred overnight.17 (s.3 (d. for C39H37ClNPRu: C. 13C{1H}-NMR (C6D6. Found: C.38 (s broad. 5. J (H. After filtration the pale brown product was recrystallized from CH2Cl2 –heptane and dried under reduced pressure.84%.H) = 6. 68. CH3). The product was recrystallized from toluene – heptane and dried under reduced pressure.3 Hz. Anal. Raw data were corrected for Lorentz. 25°C): l = 54. Ru C ). CH3).75 (m. H.00 g. 4. 3.1 Hz.

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