Five-Coordinate 16-Electron Carbene- and Vinylideneruthenium(II) Complexes Prepared from [RuCl₂(C₈H₁₂)]_n or from the New Dihydridoruthenium(IV) Compound [RuH₂Cl₂(PⁱPr₃)₂]

Abstract

The dihydridoruthenium(IV) compound [RuH2Cl2(P i Pr3)2] (2), which is obtained on treatment of [RuCl2(C8H12)] n with P i Pr3 in 2-butanol in the presence of H2, reacts with PhC⋮CH in CH2Cl2 at 25 °C to give a mixture of [RuCl2(CCHPh)(P i Pr3)2] (4) and [RuCl2(CHCH2Ph)(P i Pr3)2] (5). Both complexes 4 and 5 as well as the methylcarbene derivative [RuCl2(CHCH3)(P i Pr3)2] (6) have been isolated; moreover, compounds 2 and 5 have been characterized by X-ray crystal structure analyses.

Coupling of terminal alkynes by RuHXL2 (X=Cl or N(SiMe3)2, L=PiPr3)

“…10 and 13) was attempted through the addition of LiC"CPh to RuCl 2 L 2 (@C@CHPh) [36,37] in benzene over 2 days. Slow exchange of Cl À with PhC"C À was observed due to the insolubility of LiC"CPh in the solvent.…”

Ultraviolet Photochemistry of CoIIIL(H2O)SO3+ [L = Me6[14]dieneN4,[14]andN4] Complexes. Quandaries about the Linkage Isomerization to O-Bonded Sulfite and the Photogeneration of Cobalt(I) in Sequential Biophotonic Photolysis

“…An iodo analogue of 3 exhibits a P-Ru-P angle of 175°, 2d vs angles of ∼112°determined computationally for 2, 2a and crystallographically for [Ru(H) 2 Cl 2 (P i Pr 3 ) 2 ]. 9 Dihydrogen-dihydride tautomeric equilibria have been spectroscopically observed in other systems, and solvent effects on the position of equilibrium have been described. 6b Hydrogenolysis of 1 in the presence of strong base such as PS, or further reaction of 4, affords a route to 3.…”

Carbynehydrido- and Vinylidenehydridoosmium Complexes with Os(PCy3)2 as a Molecular Unit

“…The elemental analysis as well as the 1 H-NMR spectrum confirm that in 8, unlike in [RuHCl(ϵCCH 3 )(S)(PCy 3 ) 2 ] ϩ The more labile component is the carbene(dihydrogen) derivative 11 (see Scheme 4), which could not be separated (S ϭ OEt 2 , OH 2 ) [18] 2 ] in the ring-opening metathesis polymerimethyl protons at δ ϭ 2.01 and 1.50. The resonances for zation (ROMP) of cyclooctene but, even more remarkably, the ϭCH and ϭCMe 2 carbon nuclei appear in the 13 Cthey also catalyze the cross-olefin metathesis of cyclopen-NMR spectrum at δ ϭ 135.9 and 162.1. tene with methyl acrylate.…”

“…In the course of our continuous studies on the synthesis pounds [RuCl 2 (ϭCHR) 2 ]. [2] Since compounds of this type, in particular with PCy 3 instead of PiPr 3 as P-donor ligand, proved to be excellent catalysts for olefin metathesis (including RCM and ROMP), [3] we be-Results and Discussion came interested in studying the formation of carbene complexes [RuCl 2 (ϭCHCH 2 R)(PRЈ 3 ) 2 ] from Ru-containing Dihydrido-and Polyhydridoosmium Complexes precursors and HCϵCR in more detail.…”

“…[2] Since compounds of this type, in particular with PCy 3 instead of PiPr 3 as P-donor ligand, proved to be excellent catalysts for olefin metathesis (including RCM and ROMP), [3] we be-Results and Discussion came interested in studying the formation of carbene complexes [RuCl 2 (ϭCHCH 2 R)(PRЈ 3 ) 2 ] from Ru-containing Dihydrido-and Polyhydridoosmium Complexes precursors and HCϵCR in more detail. As a consequence we developed a convenient and very efficient one-pot synUnder the conditions under which RuCl 3 · 3 H 2 O is thesis of compounds [RuCl 2 (ϭCHCH 2 R)(PCy 3 ) 2 ] (R ϭ H, converted into the hydrido(dihydrogen) complex Ph) from ruthenium trichloride, PCy 3 , Mg, H 2 ,water,and [RuHCl(H 2 )(PCy 3 ) 2 ], [4] the reaction of OsCl 3 · 2 H 2 O with terminal alkynes as starting materials. [4] The principal ad-activated Mg and PCy 3 under H 2 takes a different course.…”