199189-24-7

Upstream product

• 124-41-4 sodium methylate 
• 67-56-1 methanol 
• 297766-43-9 [(η6-indene)(hydrido)(((C6H5)2PCH2)2)ruthenium]CF3SO3 

Downstream Products

• 297766-49-5 [(η5-indenyl)(dihydrido)(((C6H5)2PCH2)2)ruthenium]CF3SO3 
• 297766-35-9 [(η5-indenyl)(η2-dihydrogen)(((C6H5)2PCH2)2)ruthenium]CF3SO3 
• 199189-19-0 Ru(C(CO2Me)=CH2)(η(5)-indenyl)(1,2-bis(diphenylphosphino)ethane) 
• 199189-12-3 Ru((E)-C(CO2Me)=CHCO2Me)(η(5)-indenyl)(1,2-bis(diphenylphosphino)ethane) 

Relevant academic research and scientific papers

η5-Indenylruthenium(II) hydride complexes: Synthesis and protonation reactions

Hydride complexes [RuH(η5-1,2,3-C9R3R′ 4)LL′] (R=R′=H, LL′=dppm (1), dppe (2); L=L′=PMe2Ph (3); L=PPh3, L′=PMe3 (4), PMe2 Ph (5), PMePh2 (6); L=CO, L′=Psup

Protonation of η5-indenyl ruthenium hydride complexes (η5-C9H7)Ru(L2)H and η5-η6haptotropic rearrangement. X-ray crystal structures of (η5-C9H7)Ru(dppm)H and [(η6-C9H8) Ru(dppp)H]+

Protonation of indenyl complexes (η5-C9H7)Ru(dppm)H and (η5-C9H7)Ru(PPh3)2H with CF3-SO3H or HBF4·Et2O at -60°C gives the η2-dihydrogen complex [(η5-C9H7)Ru(dppm)(H2)]+and the dihydrate [(η5-C9H7)Ru(PPh3)2H2]+, respectively. Upon warming to room temperature, proton shift from the η2-H2ligand of the former to the indenyl ligand and subsequent migration of the metal fragment from the five-membered ring to the six-membered ring of the indene ligand results in the formation of the η6-indene complex [(η6-C9H8)Ru(dppm)H]+. The PPh3analogue [(η6-C9H8)Ru(PPh3)2H]+is formed in a similar fashion, but in this case, the proton shift is from Ru-H to the indenyl ligand. Low-temperature acidification of (η5-C9H7)Ru(dppe)H and (η5-C9H7)Ru (dppp)H yield mixtures of η2-dihydrogen complex and dihydride in both cases. Similar to the dppm and PPh3analogues, η6-indene complexes [(η6-C9H8)Ru(dppe)H]+and [(η6-C9H8)Ru(dppp)H]+are generated upon warming solutions of the η2-dihydrogen complex/dihydride mixtures to room temperature. In the dppp system, the η5→ η6haptotropic rearrangement only occurs after the η2-dihydrogen complex → dihydride tautomerization is nearly completed, whereas in the dppe system the two processes seem to occur simultaneously. The parent hydride complexes (η5-C9H7)Ru(L2)H can be regenerated upon deprotonation of the η6-indene complexes with Et3N. Crystal structures of (η5-C9H7)Ru(dppm)H and [(η6-C9H8)Ru(dppp)H]+have been determined by X-ray crystallography; both complexes have three-legged piano-stool structures.

Insertion reactions of alkynes into the Ru-H bond of indenylruthenium(II) hydride complexes. Mechanism of the reaction of phenylacetylene with [RuH(η5-C9H7)(dppm)] (dppm = bis (diphenylphosphino)methane)

The indenyl complexes [RuX(η5-C9H7)(dppm)] (dppm = bis(diphenylphosphino)methane, X = H, D) react with phenylacetylene to give the products of syn addition [Ru{(E)-CH=CXPh)(η5-C9H7)(dppm)] in toluene, in the temperature range 40-80 °C. The indenyl complexes [RuH(η5-C9H7)LL′] (L = L′ = PMe2Ph; L = PPh3, L′ = PMe2Ph; L = PPh3, L′ = PMe3; LL′ = dppe) and [RuH(η5-Me3C9H4)(CO)(PPh 3)] and the cyclopentadienyl complex [RuH(η5-C5H5)(dppm)] do not react with PhC≡CH, even under more forcing conditions. The complexes [RuH(η5-C9H7)LL′] (LL′ = dppe; LL′ = dppm; L = L′ = PMe2Ph; L = PPh3, L′ = PMe3; L = PPh3, L′ = PMe2Ph) and the indenyl-substituted complexes [RuH(η5-Me3C9H4)(CO)(PR 3)] (PR3 = PPh3, PiPr3) react with dimethyl acetylenedicarboxylate to give the alkenyl derivatives [Ru{(E)-C(CO2Me)=CH(CO2Me)}(η5-C 9H7)LL′] and [Ru{(E)-C(CO2-Me)=CH(CO2Me)}(η5-Me 3C9H4)(CO)(PR3)], respectively, in diethyl ether under reflux. The reaction of [RuH(η5-C9H7)LL′] with methyl propiolate yields the α-metalated alkenyl complexes [RU{C(CO2Me)=CH2}(η5-C9H 7)LL′] (LL′ = dppe, dppm; L = L′ = PMe2Ph; L = PPh3, L′ = PMe3) in refluxing diethyl ether. A kinetic study has been carried out for the reaction of the complexes [RuX(η5-C9H7)(dppm)] with phenylacetylene in toluene, by 1H and 31P(1H) NMR spectroscopy. The reactions are first order with respect to the ruthenium complex and to the alkyne. The hydride and the deutende complexes react at the same rate; intermediates are not detectable neither by kinetic studies nor by spectroscopy. The activation parameters, from rate measurements in the range 40-60 °C, are as follows:ΔH? = 17 ± 2 kcal mol-1, ΔS? = -21 ± 4 cal mol-1 K-1. An associative mechanism is proposed for the reaction, which involves the formation of an intermediate from the ruthenium complex and the alkyne under rate-determining steady-state conditions, followed by fast hydride migration and product formation. Due to the lack of reactivity of the analogous cyclopentadienyl complex [RuH(η5-C5H5)(dppm)], the reaction represents a case of indenyl effect. On the other hand, the indenyl and the cyclopentadienyl complexes react at comparable rates with the activated alkyne methyl propiolate.