343376-55-6Relevant articles and documents
Indenyl-ruthenium(II) allenylidene complexes containing terpenic substituents as precursors of optically active terminal alkynes: Scope and limitations
Cadierno, Victorio,Conejero, Salvador,Gamasa, M. Pilar,Gimeno, Jose
, p. 3060 - 3066 (2003)
The optically active allenylidene complex Ru{=C=C=C(C9H 16)}(η5-C9H7)(PPh 3)2][PF6] C(C9H16) = (1R,4S)-1,3,3-trimethyl-bicyclo[2.2.1]hept-2-ylide
Nucleophilic additions of anionic Group 6 carbene complexes on cationic indenyl-ruthenium(n) allenylidene derivatives: An easy entry to bimetallic complexes containing tr-alkynyl-carbene and vinylidene-carbene bridges
Cadierno, Victorio,Conejero, Salvador,Filar Gamasa,Gimeno, Jose
, p. 451 - 457 (2000)
The novel indenyl-ruthenium(n) allenylidene complexes [Ru{=C=C=C(R)Ph}(η5-C9H7)(PPh 3)L][PF6] (L = PMePh2, R = Ph 4a, H 4b; L = PMe2Ph, R = Ph 5) have been prepared by reaction of [RuCl(η5-C9H7)(PPri3)L] (L = PMePh2 2, PMe2Ph 3) with HCHCC(OH)(R)Ph and NaPF6 in methanol. These allenylidene derivatives as well as [Ru {=C=C=C(R)-Ph}(η5-C9H7)(PPh 3)2][PF6] (R = Ph la, H Ib) undergo regioselective nucleophilic additions of anionic Fischer type carbene complexes [Li][(CO)5M{=C(OMe)CH2}] (M = Cr, W, Mo) at the Cγ atom of the unsaturated chain to afford the neutral bimetallic σ-alkynyl derivatives [Ru(CHCC(R)Ph{CH2C(OMe)=M(CO)5})(η5-C 9H7)(PPh3)L] (L = PPh3, R = Ph, M = Cr 6a, W 6b, Mo 6c; L = PPh3, R = H, M = Cr 7a, W 7b; L = PMePh2, R = Ph, M = Cr 8a, W 8b; L = PMePh2, R = H, M = Cr 9a, W 9b; L = PMe2Ph, R = Ph, M = Cr lOa, W lOb). Protonation of these derivatives with HBF4-Et2O yields cationic vinylidene complexes [Ru(=C=C(H)C(R)Ph{CH2C(OMe)=M(CO)5})(η 5-C9H7)-(PPh3)L][BF4] lla-c, 12-15a,b which represent the first examples of bimetallic species containing a vinylidene-carbene bridge. Heating under reflux solutions of vinylidene complexes lib and 12b in acetonitrile affords the carbene derivatives [(CO)5W{=C(OMe)CH2C(R)Ph(OCH)}] (R = Ph 16a, H 16b) and the nitrile complex [Ru(N=CMe)(η5-C9H7)(PPh3) 2][BF4] 17. The diphenylallenylidene complex la regioselectively reacts with NaON to yield the σ-alkynyl derivative [Ru{G;CCPh2(C=N)}(η5-C9H 7)(PPri3)2] 18. Treatment of 18 with one equivalent of [M(CO)5(THF)] leads to the formation of the bimetallic σ-alkynyl complexes [Ru(OCCPh2{C=N-M(CO)5})-(η5-C 9H7)(PPh3)2] (M = Cr 20a, W 20b, Mo 20c). The Royal Society of Chemistry 2000.
Syntheses and characterization of indenylruthenium(II) complexes containing N,N′ donor Schiff base ligands. Molecular structures of [(η5-C9H7)Ru(PPh3)2(CH3CN)]BF4 and [(η5-C9H7)Ru(PPh3)(C5 H4-N-2-CH=N-C6H4-p-CH3)] BF4
Keisham, Sarjit Singh,Mozharivskyj, Yurij A.,Carroll, Patrick J.,Kollipara, Mohan Rao
, p. 1249 - 1256 (2004)
Reaction of the complex [(η5-C9H7) Ru(PPh3)2Cl] (1) with acetonitrile in the presence of NH4BF4 leads to formation of the complex [(η5-C9H7) Ru(PPh3)2(CH3CN)]BF4 (2). The complex (2) undergoes reactions with a series of N,N′ donor Schiff bases, viz., para -substituted N-(pyrid-2-ylmethylene)-phenylamines (ppa) in methanol yielding indenyl ruthenium(II) Schiff base complexes of formulation [(η5-C9H7)Ru(PPh3) (C5H4N-2-CH=N-C6 H4-p-X)]BF4 (3a-3e), where C9 H7=indenyl, X=H (3a), Me (3b), OMe (3c), NO2 (3d), and Cl (3e), respectively. These complexes were fully characterized on the basis of elemental analyses and NMR spectroscopy. The molecular structures of the starting complex [(η5-C9 H7)Ru(PPh3)2(CH3CN)] BF4 (2) and a representative complex [(η5 -C9H7)Ru(PPh3)(C5 H4N-CH=N-C6H4 -p-CH3)]BF4 (3b) have been established by X-ray diffraction study.
Stereoselective synthesis of chiral terminal (E)-1,3-enynes derived from the aldehydes (1R)-( - )-myrtenal and (S)-( - )-perillaldehyde using the alkynyl - Phosphonio complex [Ru{C≡CCH2(PPh3)}(η5-C 9H7)(PPh3)2][PF6] as synthon
Cadierno, Victorio,Gamasa, M. Pilar,Gimeno, José
, p. 39 - 45 (2001)
Treatment of alkynyl-phosphonio complex [Ru{C=CCH2(PPh3)}(η5-C9H 7)(PPh3)2][PF6] (1) with LinBu gives the ylide-alkynyl derivative [Ru{C≡CC(H)=PPh3}(η5-C9H 7)(PPh3)2] (2), which reacts in situ with the optically active aldehydes (1R)-(-)-myrtenal and (S)-(-)-perillaldehyde via a Wittig process to afford σ-alkynyl complexes [Ru{C≡CC(H)=C(H)C9H13}(η5-C 9H7)(PPh3)2] 3 and 7 respectively. Whereas compound 3 has been obtained stereoselectively as the pure E stereoisomer, complex 7 has been synthesized as a mixture of the corresponding E and Z isomers (ca. 4:1 ratio). Protonation of 3 and 7 with HBF4·Et2O yields the cationic alkenyl-vinylidene derivatives (E)-[Ru{=C=C(H)C(H)=C(H)C9H13}(η5-C 9H7)(PPh3)2][BF4] (4, 8), which react with acetonitrile at reflux to afford the nitrile complex [Ru(N≡CMe)(η5-C9H7)(PPh 3)2][BF4] (6), and the corresponding terminal 1,3-enynes (E)-HC≡CC(H)=C(H)C9H13 5 and 9 respectively.
Unexpected coupling between an η5-indenyl ligand and alkenyl-vinylidene fragments: Synthesis of unprecedented (η6-indene)ruthenium(II) metallacycles
Cadierno, Victorio,Conejero, Salvador,Diez, Josefina,Gamasa, M. Pilar,Gimeno, Jose,Garcia-Granda, Santiago
, p. 840 - 841 (2007/10/03)
Vinylidene complexes [Ru{=C=C(H)CR1R2CH2C(Me)= CH2}(η5-C9H7)(PPh 3)2][BF4] undergo an intramolecular coupling between the alkenyl-vinylidene frag
In search of optically active γ-keto acetylenes via regioselective coupling of allenylidene groups and cyclic enolates
Cadierno, Victorio,Conejero, Salvador,Gamasa, M. Pilar,Gimeno, José,Falvello, Larry R.,Llusar, Rosa M.
, p. 3716 - 3726 (2008/10/08)
An efficient synthetic approach of γ-keto acetylenes based on the regio- and diastereoselective propargylic alkylation of 2-propyn-1-ols with methyl ketones was discussed. The synthetic methodology constituted an alternative to the well-known Nicholas cou
Efficient synthetic routes to terminal γ-keto-alkynes and unsaturated cyclic carbene complexes based on regio- and diastereoselective nucleophilic additions of enolates on ruthenium(II) indenyl allenylidenes
Cadierno, Victorio,Conejero, Salvador,Gamasa, M. Pilar,Gimeno, José,Pérez-Carre?o, Enrique,García-Granda, Santiago
, p. 3175 - 3189 (2008/10/08)
Ruthenium(II) indenyl allenylidene complexes [Ru{=C=C=C(R1)Ph}(η5-C9H7) (PPh3)2] [PF6] (R1 = Ph (1), H (2)) regioselectively react with lithium enolates LiCH2COR2 (R2 = Ph, iPr, Me, Fc, (E)-CH=CHPh) at the Cγ atom to yield the neutral σ-alkynyl derivatives [Ru{C≡CC(R1)Ph(CH2COR2)} (η5-C9H7)(PPh3)2] (3a-e, 4a-d). Protonation of 3a-e and 4a-d with HBF4·Et2O affords the cationic vinylidene derivatives [Ru{=C=C(H)C(R1)Ph(CH2COR2)}(η5- C9H7)(PPh3)2] [BF4] (5a-e, 6a-d), which can be easily demetalated, by treatment with acetonitrile, to yield the terminal γ-keto-substituted alkynes HC≡CC(R1)Ph(CH2COR2) (7a-e, 8a-d) and the nitrile complex [Ru(N≡CMe)(η5-C9H7) (PPh3)2][BF4] (9). The addition of lithium enolates LiCH2COR (R = Ph, iPr, Me) on the optically active allenylidene complex [Ru{=C=C=C(C9H16)}(η5-C9 H7)(PPh3)2][PF6] (12; C(C9H16) = (1R)-1,3,3-trimethylbicyclo[2.2.1]hept-2-ylidene) proceeds in a regio- and diastereoselective manner, affording σ-alkynyl derivatives [Ru{C≡CC(C9H16)(CH2COR)} (η5-C9H7)(PPh3)2] (13a-c). The X-ray crystal structure of 13b shows that these enolate additions take place on the less sterically congested exo face of the allenylidene chain. Chiral alkynes HC≡CC(C9H16)(CH2COR) (15a-c) have been also prepared from 13a-c via initial protonation with HBF4·Et2O and subsequent treatment of the resulting vinylidenes 14a-c with acetonitrile. Cyclic alkenyl derivatives [Ru{C=CHC(R1)(R2)CH=C(R3)O} (η5-C9H7)(PPh3)2] (R1 = R2 = Ph, R3 = Ph (18a), iPr (18b); R1R2 = C9H16, R3 = Ph (20)) have been obtained by treatment of dichloromethane solutions of σ-alkynyl complexes 3a,b and 13a with catalytic amounts of AlCl3 at room temperature. Protonation of these species affords the cyclic carbenes [Ru{=CCH2C(R1)(R2)CH=C(R3)O}- (η5-C9H7)(PPh3)2] [BF4] (19a,b, 21).
A novel route to functionalized terminal alkynes through η1-vinylidene to η2-alkyne tautomerizations in indenyl-ruthenium(II) monosubstituted vinylidene complexes: Synthetic and theoretical studies
Cadierno, Victorio,Gamasa, M. Pilar,Gimeno, José,Pérez-Carre?o, Enrique,García-Granda, Santiago
, p. 2821 - 2832 (2008/10/08)
Heating under reflux solutions of the monosubstituted vinylidene complex [Ru{=C=C(H)-Ph}(η5-C9H7)(PPh 3)2][PF6] (1) in nitriles yields the complexes [Ru(N≡CR)(η5-C9H7)(PPh 3)2]-[PF6] (R = Me (2a), Et (2b), Ph (2c)) and phenylacetylene. The process proceeds via an initial η1-vinylidene-η2-alkyne tautomerization followed by the displacement of the coordinated π-alkyne by the solvent. Vinylidene complexes [Ru{=C=C(H)R}(η5-C9H7)(PPh 3)2][PF6] (R = (η5-C5H4)Fe(η5-C 5H5) (3), 4-NO2-C6H4 (4)) also react with acetonitrile to yield the nitrile derivative 2a and the corresponding terminal alkynes HC≡CR. Cationic alkenyl-vinylidene derivatives [RU{=C=C(H)CH=CR1R2}(η5-C9H 7)(PPh3)2][BF4] (R1 = R2 = Ph (7a), R1 = H; R2 = 4-OMe-C6H4 [(Z)-Tb], 4-NO2-C6H4 [(E,Z)-7c], (η5-C6H4)Fe(η5-C 5H5) [(E)-7d]) behave similarly. Thus, the treatment of 7a-d with acetonitrile at reflux results in the formation of complex 2a and the liberation of the corresponding terminal 1,3-enyne HC≡CCH=CR1R2 (8a-d). The formation of the enynes 8b-d is stereoselective, giving rise to the E stereoisomer. The allenylidene complex [Ru{=-C=C-C(C13H20)}(η5-C9H 7)(PPh3)2][PF6] (9), containing the bicyclic [3.3.1]non-2-en-9-ylidene moiety C13H20, reacts with NaC≡CH in THF at -20°C to yield the neutral σ-alkynyl derivative [Ru{C≡CC(C≡CH)C13H20}(η5-C 9H7)(PPh3)2] (10) in a regioselective manner. Protonation of 10 with HBF4·Et2O, in diethyl ether at -20°C, affords the vinylidene complex [Ru{=C=C(H)C(C≡CH)C13H20}(η5-C 9H7)(PPh3)2][BF4] (11), which can be easily demetalated by heating in refluxing acetonitrile to give 2a and the unprecedented diyne (HC≡C)2CC13H20 (12). These demetalation processes allow the quantitative recovery of the metal auxiliary as the labile complex 2a, which can be used as starting material for further reactions. Ab initio molecular orbital calculations on the η1-vinylidene to η2-alkyne tautomerization have been performed. It is shown that the process proceeds through a 1,2-[H] shift mechanism showing that the conversion requires an energy barrier of 29.9 kcal/ mol. This is a value low enough to be overcome under the experimental reaction conditions allowing the formation of the labile η2-alkyne complex and the subsequent exchange of the coordinated alkyne by acetonitrile.
