Synthesis and reactivity of dimetallacyclopentenone complexes [Ru2(CO)(μ-CO){μ-C(O)CR1CR2}(η-C5H5)2] (R1 = Me or Ph; R2 = CO2Me)

King, Philip; Knox, Selby A. R.; McCormick, Gillian J.; Orpen, A. Guy

doi:10.1039/b003156i

Cited by 14 publications

(13 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is also noteworthy that the insertion of CO into a Ru–C bond was not observed in this study, in contrast to the ruthenium clusters supported by Cp (Cp = η 5 -C 5 H 5 ) or CO ligands, in which the insertion of CO into a Ru–C bond at a multinuclear site often took place . The electron-donating Cp* groups would cause enhanced back-donation to the π*(CO) orbital, strengthening the Ru–CO bond.…”

Section: Discussioncontrasting

confidence: 54%

Synthesis of an Electron-Deficient Triruthenium Hydrido Complex Having a Bridging Carbonyl Ligand: Influence of a CO Ligand on the Properties and Reactivities of a Hydrido Cluster

et al. 2017

View full text Add to dashboard Cite

A novel triruthenium hydrido cluster, (Cp*Ru)3(μ3-H)(μ-H)2(μ-CO) (4; Cp* = η5-C5Me5), having a bridging CO ligand was synthesized by the reaction of {Cp*Ru(μ-H)}3(μ3-O) (3) with methanol. Upon introduction of a CO ligand, the cyclic voltammogram of 4 demonstrated a significant shift of the redox potential in the positive direction in comparison to a pentahydrido complex, {Cp*Ru(μ-H)}3(μ3-H)2 (1), which adopts the same 44-electron configuration. Owing to its coordinatively unsaturated nature, 4 readily reacted with butadiene, terminal alkynes, and alkenes similarly to the parent pentahydrido complex 1. However, the reactivity was slightly different from that of 1, and the influence of the CO ligand at the triruthenium site was evaluated by the reaction of various unsaturated hydrocarbons. The reaction of 4 with 1,3-dienes yielded a diene adduct, {Cp*Ru(μ-H)}3(μ-η2:η2-s-cis-H2CCRCHCH2)(CO) (5a, R = H; 5b, R = Me) without elimination of dihydrogen. In the same manner as for 1, 4 reacted with phenylacetylene to yield a μ3-η2:η2(⊥)-alkyne complex, (Cp*Ru)3(μ-H){μ3-η2:η2(⊥)-PhCCH}(μ3-CO) (7a); in contrast, an isomeric μ3-pentenylidene complex, (Cp*Ru)3(μ-H){μ3-η2-CC(nPr)H}(μ-CO) (9b), was obtained by reaction with 1-pentyne. A series of products was obtained by the reaction of 4 with ethylene molecules. A μ3-ethylidyne complex, (Cp*Ru)3(μ-H)2(μ3-CMe)(μ-CO) (11), was initially formed, accompanied by the formation of ethane at ambient temperature. The treatment of 11 with ethylene resulted in the removal of hydrido ligands, affording a μ3-vinylidene complex, (Cp*Ru)3(μ-H)(μ3-η2-CCH2)(μ-CO) (9a). At higher temperatures, a second ethylene molecule was incorporated in the triruthenium plane and an equilibrated mixture of a μ3-ethylidyne−μ-ethylidyne complex, (Cp*Ru)3(μ-H)(μ-CMe)(μ3-CMe)(μ-CO) (13), and μ3-ethylidyne−μ-vinyl complex, (Cp*Ru)3(μ-H)(μ3-CMe)(μ-η2-CHCH2)(μ-CO) (12), was obtained. The formation of a μ3-η3-C3 ring on the Ru3 plane was observed upon the thermolysis of the equilibrated mixture at 180 °C, which clearly demonstrates the coupling of the two C2 moieties placed on each face of the triruthenium plane.

show abstract

Section: Discussioncontrasting

confidence: 54%

Synthesis of an Electron-Deficient Triruthenium Hydrido Complex Having a Bridging Carbonyl Ligand: Influence of a CO Ligand on the Properties and Reactivities of a Hydrido Cluster

et al. 2017

View full text Add to dashboard Cite

show abstract

“…Unfortunately, these resonances could not be located in the spectrum of 10 , probably due to broadening effects. Although we are not aware of previous examples for a coordinated phosphide-acyl ligand analogous to that proposed here, we note the strong structural relationship with several alkenyl-acyl or alkenyl-iminoacyl and related ligands bridging dimetal centers (Chart ). − Interestingly, some of these acyl complexes undergo decarbonylation and deinsertion reactions comparable to those relating our complexes, a matter to be discussed below.…”

Section: Resultsmentioning

confidence: 53%

“…We should note that the observed transformations 6a → 10 → 3a discussed in the preceding sections actually are an exact representation of the sequence C → D → 3 here proposed. Moreover dimetal complexes having dimetallacyclopentenone rings also offer independent precedents of related transformations, not only of the coordination of the CC double bond (analogous to the C → D step), but also of deinsertion of CO to give dimetallacyclobutene rings (analogous to the D → 3 step). , Finally, when L = CNXyl, the nucleophilic attack of the carbanionic atom in the corresponding intermediate B would preferentially occur at the isocyanide, rather than at a carbonyl ligand. Although the origin of this chemoselectivity is not clear to us at the moment, we note that an analogous selectivity has been reported in the related reactions of the thiolate complexes [FeCp(SPh)(CNMe)(CX)] (X = O, S) with DMAD to give the thiametallacyclopentenimine derivatives [FeCp{κ 1 ,η 1 -SPhCRCRC(NMe)}(CX)], derived from the specific binding of the alkyne to the isocyanide, rather than to the carbonyl or thiocarbonyl ligands .…”

Section: Resultsmentioning

confidence: 99%

Reactivity of the Phosphinidene-Bridged Complexes [Mo₂Cp(μ-κ¹:κ¹,η⁵-PC₅H₄)(η⁶-1,3,5-C₆H₃^tBu₃)(CO)₂] and [Mo₂Cp₂(μ-PH)(η⁶-1,3,5-C₆H₃^tBu₃)(CO)₂] toward Alkynes: Multicomponent Reactions in the Presence of Ligands

et al. 2012

View full text Add to dashboard Cite

The cyclopentadienylidene-phosphinidene complex [Mo 2 Cp(μ-κ 1 :κ 1 ,η 5 -PC 5 H 4 )(η 6 -HMes*)(CO) 2 ] (1) (Cp = η 5 -C 5 H 5 ; Mes* = 2,4,6-C 6 H 2 t Bu 3 ) reacted with RCCR′ in refluxing toluene solutions to give the corresponding phosphide derivatives [Mo 2 Cp{μ-κ 1 ,η 5 :κ 1 ,η 1 -(C 5 H 4 )PCRCR′}(η 6 -HMes*)(CO) 2 ] (R = R′ = CO 2 Me; R = H, R′ = CO 2 Me, p-tol), displaying a phosphametallacyclobutene ring. In contrast, the phosphinidene complex [Mo 2 Cp 2 (μ-PH)(η 6 -HMes*)(CO) 2 ] (2) reacted with MeO 2 CCCCO 2 Me at room temperature to give first the monocarbonyl phosphide-acyl complex [Mo 2 Cp 2 {μ-κ 1 :κ 1 ,η 3 -PHC(CO 2 Me)C(CO 2 Me)C(O)}(η 6 -HMes*)(CO)], the latter evolving progressively to the isomeric dicarbonyl [Mo 2 Cp 2 (μ-κ 1 :κ 1 ,η 1 -PHC(CO 2 Me)C(CO 2 Me)}(η 6 -HMes*)-(CO) 2 ] (Mo−P ca. 2.57 Å). When different ligands such as CO, PMe 3 , P(OMe) 3 , or CNXyl were added at room temperature to toluene solutions containing compound 1 and different alkynes, relatively fast multicomponent reactions took place to give with good yields the corresponding phosphide-acyl complexes [Mo 2 Cp{μ-κ 1 ,η 5 :κ 1 ,η 1 -(C 5 H 4 )PCRCR′C(O)}(η 6 -HMes*)(CO) 2 ] (R = R′ = CO 2 Me; R = H, R′ = CO 2 Me, p-tol), and [Mo 2 Cp{μ-κ 1 ,η 5 :κ 1 ,η 1 -(C 5 H 4 )PC(CO 2 Me)C(CO 2 Me)C(O)}(η 6 -HMes*)(CO)(L)] (L = PMe 3 , P(OMe) 3 ) or the related phosphide-iminoacyl derivatives [Mo 2 Cp{μ-κ 1 ,η 5 :κ 1 ,η 1 -(C 5 H 4 )PCRCR′C(NXyl)}(η 6 -HMes*)(CO) 2 ] (Xyl = 2,6-C 6 H 3 Me 2 ; R = R′ = CO 2 Me; R = H, R′ = CO 2 Me, C(O)Me), respectively, all of them displaying five-membered phosphametallacyclopentenone or phosphametallacyclopentenimine rings. Separate experiments revealed that the latter complexes (R = R′ = CO 2 Me) could be decarbonylated photochemically to yield the corresponding monocarbonyls [Mo 2 Cp{μ-κ 1 ,η 5 :κ 1 ,η 3 -(C 5 H 4 )PC-(CO 2 Me)C(CO 2 Me)C(X)}(η 6 -HMes*)(CO)] (X = O, NXyl), the latter rearranging at room temperature to give the corresponding phosphametallacyclobutene isomers [Mo 2 Cp{μ-κ 1 ,η 5 :κ 1 ,η 1 -(C 5 H 4 )PC(CO 2 Me)C(CO 2 Me)}(η 6 -HMes*)-(CO)(CX)]. A side product was also formed during the photochemical treatment of the dicarbonyl substrate, it being finally isolated after chromatographic workup as the alkenylphosphide-chloride complex [Mo 2 CpCl{μ-κ 1 ,η 5 :κ 1 ,η 2 -(C 5 H 4 )PC-(CO 2 Me)CH(CO 2 Me)}(η 6 -HMes*)(CO)] (Mo−P = 2.553(2) and 2.436(2) Å ́).

show abstract

“…Thus, N(1) displays a sp 3 hybridization and, accordingly, the sum of the angles at N(1) is far from 360°, as expected for sp 2 hybridization. Allylidene ligands bridging two metal centers in a μ-η 1 :η 3 fashion are not uncommon in organometallic chemistry, and they typically consist of a hydrocarbyl C 3 chain . However, the derivatization of the vinyliminium ligand represents a unique strategy to access doubly substituted allylidene structures stereoselectively.…”

Section: Resultsmentioning

confidence: 99%

Diiron Complexes with a Bridging Functionalized Allylidene Ligand: Synthesis, Structural Aspects, and Cytotoxicity

et al. 2020

View full text Add to dashboard Cite

Regio-and stereo-selective nucleophilic attack of cyanide (from NBu 4 CN) to cationic diironaffords nitrile-aminoallylidene derivatives, 2a-f, in good to excellent yield. The analogous reaction of [1g]CF 3 SO 3 , comprising two different N-substituents, gives 4 (63%) as a mixture of two stereoisomers.The new products [1g]CF 3 SO 3 , 2a-f and 4 were characterized by IR and NMR spectroscopy, and in a number of cases by IR-spectroelectrochemistry and single crystal X-ray diffraction. The allylidene complexes are air-stable and robust in aqueous solution, however, in general they undergo oxidation within a biologically relevant range of potentials. DFT calculations were carried out to rationalize the observed stereo-selectivity of the synthesis reaction and other structural and thermodynamic aspects.The cytotoxicity of 2a-f was assessed on cisplatin sensitive and resistant human ovarian carcinoma (A2780 and A2780cisR) cell lines, and human embryonic kidney (HEK-293) cells. Experiments reveal that treatment with the compounds leads to ROS production, with an absence of direct interactions with double stranded DNA (calf thymus) and bovine serum albumin.

show abstract

Synthesis and reactivity of dimetallacyclopentenone complexes [Ru2(CO)(μ-CO){μ-C(O)CR1CR2}(η-C5H5)2] (R1 = Me or Ph; R2 = CO2Me)

Abstract: 8). The structures of the unusual complexes 6 and 7 have been determined by X-ray diffraction studies. Complexes 5, 6 and 7 are shown to be formed from 2i,j via independent pathways.

Cited by 14 publications

References 12 publications

Synthesis of an Electron-Deficient Triruthenium Hydrido Complex Having a Bridging Carbonyl Ligand: Influence of a CO Ligand on the Properties and Reactivities of a Hydrido Cluster

Synthesis of an Electron-Deficient Triruthenium Hydrido Complex Having a Bridging Carbonyl Ligand: Influence of a CO Ligand on the Properties and Reactivities of a Hydrido Cluster

Reactivity of the Phosphinidene-Bridged Complexes [Mo₂Cp(μ-κ¹:κ¹,η⁵-PC₅H₄)(η⁶-1,3,5-C₆H₃^tBu₃)(CO)₂] and [Mo₂Cp₂(μ-PH)(η⁶-1,3,5-C₆H₃^tBu₃)(CO)₂] toward Alkynes: Multicomponent Reactions in the Presence of Ligands

Diiron Complexes with a Bridging Functionalized Allylidene Ligand: Synthesis, Structural Aspects, and Cytotoxicity

Contact Info

Product

Resources

About

Synthesis and reactivity of dimetallacyclopentenone complexes [Ru2(CO)(μ-CO){μ-C(O)CR1CR2}(η-C5H5)2] (R1 = Me or Ph; R2 = CO2Me)

Abstract: 8). The structures of the unusual complexes 6 and 7 have been determined by X-ray diffraction studies. Complexes 5, 6 and 7 are shown to be formed from 2i,j via independent pathways.

Cited by 14 publications

References 12 publications

Synthesis of an Electron-Deficient Triruthenium Hydrido Complex Having a Bridging Carbonyl Ligand: Influence of a CO Ligand on the Properties and Reactivities of a Hydrido Cluster

Synthesis of an Electron-Deficient Triruthenium Hydrido Complex Having a Bridging Carbonyl Ligand: Influence of a CO Ligand on the Properties and Reactivities of a Hydrido Cluster

Reactivity of the Phosphinidene-Bridged Complexes [Mo2Cp(μ-κ1:κ1,η5-PC5H4)(η6-1,3,5-C6H3tBu3)(CO)2] and [Mo2Cp2(μ-PH)(η6-1,3,5-C6H3tBu3)(CO)2] toward Alkynes: Multicomponent Reactions in the Presence of Ligands

Diiron Complexes with a Bridging Functionalized Allylidene Ligand: Synthesis, Structural Aspects, and Cytotoxicity

Contact Info

Product

Resources

About

Reactivity of the Phosphinidene-Bridged Complexes [Mo₂Cp(μ-κ¹:κ¹,η⁵-PC₅H₄)(η⁶-1,3,5-C₆H₃^tBu₃)(CO)₂] and [Mo₂Cp₂(μ-PH)(η⁶-1,3,5-C₆H₃^tBu₃)(CO)₂] toward Alkynes: Multicomponent Reactions in the Presence of Ligands