Selective Cα–Cβ bond cleavage by water in allenylidene and alkenylvinylidene ruthenium complexes

Bianchini, Claudio; Peruzzini, Maurizio; Zanobini, Fabrizio; López, Carlos; Ríos, Isaac de los; Romerosa, Antonio

doi:10.1039/a900011i

Cited by 43 publications

(22 citation statements)

References 22 publications

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“…b) Neutral octahedral ruthenium(II) fac,cis ‐[RuCl 2 (=C=C=CPh 2 )(PNP)] {PNP= MeCH 2 CH 2 N(CH 2 CH 2 PPh 2 ) 2 },18 [RuCl 2 (=C=C=CPh 2 )(CO)(Sb i Pr 3 ) 2 ]19 and square‐planar iridium(I) trans ‐[IrF(=C=C=CPh 2 )(P i Pr 3 ) 2 ]20 complexes.…”

Section: Structural and Spectroscopic Propertiesmentioning

confidence: 99%

Recent Developments in the Reactivity of Allenylidene and Cumulenylidene Complexes

Cadierno

Gamasa

Gimeno

2001

Eur. J. Inorg. Chem.

200

117

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Allenylidene and higher cumulenylidene complexes [M]=C(=C)n=CR1R2 (n = 1, 2, 3) have continuously gained significance in the context of transition metal carbene chemistry. Important developments which have been disclosed during the last two years are reviewed. These include a variety of stoichiometric and catalytic reactions of allenylidene complexes and their utility in organic synthesis. The related chemistry of butatrienylidene (n = 2) and pentatetraenylidene (n = 3) complexes as well as theoretical studies are also reviewed.

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Section: Structural and Spectroscopic Propertiesmentioning

confidence: 99%

Recent Developments in the Reactivity of Allenylidene and Cumulenylidene Complexes

Cadierno

Gamasa

Gimeno

2001

Eur. J. Inorg. Chem.

200

117

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“…Such a small singlet may be attributable to the carbonyl compound [RuTpCl(CO)(thp)], [20] presumably produced by reaction of the allenylidene with water released from Selegue's reaction. Similar addition reactions of water have already been described for other cationic [21] and neutral [22] ruthenium(II) allenylidene complexes. Compound 11 was characterised by NMR spectroscopy.…”

Section: Reaction Of 1 With Terminal Alkynes and 11-diphenyl-2-propymentioning

confidence: 56%

Formation of Oxaphosphacarbenes by Reaction of [RuTpCl(PPh₃)(thp)] with Terminal Alkynes and a Propargylic Alcohol

et al. 2010

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The reaction of [TpRuCl(PPh3)2] [Tp = hydrotris(pyrazolyl)borate] with P(CH2OH)3 (thp) afforded [TpRuCl(PPh3)(thp)] (1). Compound 1 heated at reflux in NCMe yielded the cationic compound [TpRu(NCMe)(PPh3)(thp)]Cl (2). The reaction of 1 with terminal alkynes R–C≡CH [R = Ph, p‐C6H4Me, Si(Me)3, EtC(O)O] and with the propargylic alcohol [Ph2(OH)C–C≡CH] in methanol gave the new metallacyclic cationic carbenes [TpRu{κ2‐(C,P)=C(CH2R′)OCH2P(CH2OH)2}(PPh3)]Cl [R′ = Ph (3a), p‐C6H4Me (4a), H (5a), MeC(O)O (6a)] and [TpRu{κ2‐(C,P)=C(CH=CPh2)OCH2P(CH2OH)2}(PPh3)]Cl (7a), respectively. When methanolic solutions of compounds 3a–5a were heated at reflux for several hours, the compounds eliminate formaldehyde to afford the new carbene complexes [RuTp{κ2‐(C,P)=C(R″)OCH2PH(CH2OH)}(PPh3)]Cl [R″ = CH2Ph (3b), CH2C6H4Me (4b), CH3 (5b), respectively]. Compound 7a showed a very high tendency to eliminate formaldehyde. As a result, the carbene [RuTp{κ2‐(C,P)=C(HC=CPh2)OCH2PH(CH2OH)}(PPh3)]Cl (7b) formed is always present during the synthesis of 7a. When heating at reflux in methanol was sufficiently prolonged, pure 7b was obtained. When the reaction of 1 with R–C≡CH [R = Ph, p‐C6H4Me, (Me)3Si] and with Ph2(OH)CC≡CH was performed in refluxing toluene, the neutral oxaphosphacarbene complexes [TpRuCl{κ2‐(C,P)=C(CH2R)OCH2P(CH2OH)2}] [R = Ph (8), p‐C6H4Me (9), (Me)3Si (10)] and [TpRuCl{κ2‐(C,P)=C(CH=CPh2)OCH2P(CH2OH)2}] (11) were obtained. Compound 9 was structurally characterised by X‐ray diffraction analysis.

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“…[15b, 22] To the best of our knowledge, the results obtained here represent the first report about the formation of Ru II carbonyls from chelating bipyridine-alkyne ligands. This finding is very surprising, since the intended bipyridine N,N-chelation was assumed to prevail over the alkyne decomposition.…”

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confidence: 74%

Towards Ruthenium‐Based Building Blocks for CuAAC Click Reactions: Challenges in Generating Ruthenium(II) Polypyridine Alkynes

et al. 2015

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Ag+ -free complexation of alkyne-bipyridines at ruthenium(II) polypyridine centers proceeds with surprisingly low yields. The alkyne-bipyridine-substituted ruthenium(II) polypyridine complexes in this work were characterized by NMR spectroscopy, ESI spectrometry, and single-crystal X-ray structural analysis. A detailed analysis of the side products revealed an unexpected carbon-carbon alkyne bond splitting

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Selective Cα–Cβ bond cleavage by water in allenylidene and alkenylvinylidene ruthenium complexes

Cited by 43 publications

References 22 publications

Recent Developments in the Reactivity of Allenylidene and Cumulenylidene Complexes

Recent Developments in the Reactivity of Allenylidene and Cumulenylidene Complexes

Formation of Oxaphosphacarbenes by Reaction of [RuTpCl(PPh₃)(thp)] with Terminal Alkynes and a Propargylic Alcohol

Towards Ruthenium‐Based Building Blocks for CuAAC Click Reactions: Challenges in Generating Ruthenium(II) Polypyridine Alkynes

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Selective Cα–Cβ bond cleavage by water in allenylidene and alkenylvinylidene ruthenium complexes

Cited by 43 publications

References 22 publications

Recent Developments in the Reactivity of Allenylidene and Cumulenylidene Complexes

Recent Developments in the Reactivity of Allenylidene and Cumulenylidene Complexes

Formation of Oxaphosphacarbenes by Reaction of [RuTpCl(PPh3)(thp)] with Terminal Alkynes and a Propargylic Alcohol

Towards Ruthenium‐Based Building Blocks for CuAAC Click Reactions: Challenges in Generating Ruthenium(II) Poly­pyridine Alkynes

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Formation of Oxaphosphacarbenes by Reaction of [RuTpCl(PPh₃)(thp)] with Terminal Alkynes and a Propargylic Alcohol

Towards Ruthenium‐Based Building Blocks for CuAAC Click Reactions: Challenges in Generating Ruthenium(II) Polypyridine Alkynes