137039-45-3

Upstream product

• 15529-49-4 tris(triphenylphosphine)ruthenium(II) chloride 
• 917-92-0 3,3-Dimethylbut-1-yne 

Downstream Products

• 125615-90-9 RuCl(CO)(PPh₃)2(C(CC-t-Bu)=CH-t-Bu) 
• 125615-90-9 [RuCl(C(CCtBu)CHtBu)(CO)(triphenylphosphine)2] 

Relevant academic research and scientific papers

Some organometallic chemistry of ruthenium(II)

Stoichiometric and catalytic reactions of Ru(II) phosphine complexes with alkynes, olefins, and enynes are described.The hydride complex RuCl(CO)H(PPh3)3 (1) reacts with the double bond of a cis-enyne whereas it reacts with triple bonds of trans-enynes.Metathesis of vinyl silanes with olefins are catalyzed by 1 where β-Si elimination is the key step.Dimerizations of t-Bu- and Me3Si-substituted acetylenes into the corresponding butatrienes are catalyzed by Ru(II) active species as studied by isolation of the intermediates.A model reaction for the crucial step of the catalytic cycle, formation of a Ru vinylidene complex from acetylene, has been fully simulated by ab initio-MO calculations.Keywords: Ruthenium; Olefins; Alkynes; Catalysis; Crystal structure; MO calculations

Acetylene π-coordination, slippage to σ-coordination, and 1,2-hydrogen migration taking place on a transition metal. The case of a Ru(II) complex as studied by experiment and ab initio molecular orbital simulations

The behavior of an acetylene molecule in the coordination sphere of transition metals has been probed by the reactions of RuX2(PPh3)3 (X = Cl, Br) with tert-butylacetylene to give vinylidene complexes of the formula RuX2(PPh3)2(C=CHtBu). IR and NMR data have indicated that the initial product of this reaction is a mixture of two complexes each of which has a vinylidene unit and nonequivalent cis-bis(phosphine) ligands. In solution, these kinetic products gradually isomerize to the final trans-bis(phosphine) complex. The structure of this five-coordinated and thermodynamically stable complex (X = Br) was determined by X-ray crystallographic analysis to have a quasi trigonal-bipyramidal conformation with the two phosphines occupying axial positions. The potential surface for the transformation of coordinated acetylene to vinylidene was calculated by the ab initio molecular orbital method. The primary process was concluded to be a slippage of the η2-CC coordinated alkyne to the η2-CH coordinated complex via a transition state with an η1-acetylene and a side-on acetylene. The η2-CH complex undergoes 1,2-hydrogen migration within the acetylene unit, whose transition state is the highest point of the whole process, giving finally the thermodynamically metastable vinylidene complex with a cis-bis(phosphine). The isomeric vinylidene ruthenium(II) complex with trans-bis(phosphine) has been calculated to be the final product and thermodynamically most stable form of this reaction system. The role of the metal in the present rearrangement is discussed on the basis of the localized molecular orbital analysis of the key intermediates.

Regio-and stereocontrolled dimerization of tert-butylacetylene to (Z)-1,4-Di-tert-butylbutatriene by ruthenium catalysis. Reaction mechanism involving alkynyl-vinylidene coupling and rearrangement of the metal-bound C4 unit

Ruthenium complexes, Ru(cod)(cot) (cod = 1,5-cyclooctadiene, cot = cyclooctariene) and Ru(CO)(PPh3)3(H)2 (1), catalyze the dimerization of tert-butylacetylene to (Z)-1,4-di-tert-butylbutatriene ((Z)-dbb). In the case of the Ru(cod)(cot) catalyst, the addition of bulky tertiary phosphines is an essential factor to effect good selectivity to dbb, the byproducts being isomers of 1,3-enynes. From the reaction of 1 with tert-butylacetylene, Ru(CO)(PPh3)3(H)(C≡CtBu) was isolated, which reacted further with HC≡CtBu to give Ru(CO)(PPh3)3(C≡CtBu)2 (3). The halogen analogue of this complex RuX2(PPh3)3, reacted with HC≡CtBu to give vinylidene comPlexes RuX2(PPh3)2(C=CHtBu) (11a, X = Cl; 11b, X = Br). Reaction of 11a with a calculated amount of LiC≡CtBu followed by bubbling of CO yielded RuCl(CO)(PPh3)3{C(C≡CtBu)=CH tBu} (12) where the C≡CtBu group and tBu are mutually cis to each other with respect to the double bond of the C4 unit. Complex 12 in tenzene decomposed at 50°C releasing the C4 chain as (Z)-dbb. From these reactions, the mechanism for the catalytic production of (Z)-dbb has been derived. The X-ray structure of 12 is reported.