Cyclic oxycarbene and vinylidene complexes of ruthenium with (PP) and (NN) type ligands

Efficient endo Cycloisomerization of Terminal Alkynols Catalyzed by a New Ruthenium Complex with 8‐(Diphenylphosphino)quinoline Ligand and Mechanistic Investigation

“…Indeed, the reaction proceeded smoothly to produce the above-mentioned newly formed complex quantitatively within 9h,w hich was isolated in 95 %y ield and identified to be the 3-benzoxepine derivatized seven-membered ruthenium oxacyclocarbene complex 12 (Scheme 3). Numerous oxacyclocarbene complexes have been prepared previously from the reactions of various transition-metal complexesw ith terminal w-alkynols, [20,[23][24][25][26] including an umber of ruthenium oxacyclocarbene complexes. [20,25] The structure of complex 12 has been confirmed by X-ray diffraction.…”

“…Numerous oxacyclocarbene complexes have been prepared previously from the reactions of various transition-metal complexesw ith terminal w-alkynols, [20,[23][24][25][26] including an umber of ruthenium oxacyclocarbene complexes. [20,25] The structure of complex 12 has been confirmed by X-ray diffraction. Figure 4s hows the X-ray structure for the cation of 12,f rom whichw ec an see that the Ru centera dopts ad istorted octahedral geometry consisting of two DPPQ ligands chelating to Ru nearly perpendicularly,o ne chlorine ligand, and one oxacarbene ligand.The Patom of one of the DPPQ ligands is trans to the Cl ligand (P(1)-Ru(1)-Cl(1), 167.48 (3)8), whereas the Na tom is trans to the Pa tom of the otherD PPQ ligand (N(1)-Ru(1)-P(2), 172.67 (7)8).…”

“…The Ru=Cb ond length of 1.937 (3) is similart o those of other reportedr utheniumo xacyclocarbene complexes. [20,25,27] Complex 12 was also characterized by multinuclear NMR spectroscopy and elementala nalysis. Consistent with the solidstate structure, the 31 P{ 1 H} NMR spectrum (in CD 2 Cl 2 )o f12 showed two doublet signals at d = 58.6 and 49.5 ppm (J(PP) = 31.3 Hz) fort he two inequivalent phosphine groups.…”

“…[20, 25f-j, l, m] The 13 C{ 1 H} NMR spectrum displayed aR u =Cs ignal at d = 321.6 ppm ( 2 J(PC) = 11.2 Hz), in agreement with those observed for other rutheniumo xacyclocarbene complexes. [25,26] [25f, h, k] Os, [26b] and Re [26a] complexes with the aliphatic alkynols. To the best of our knowl-edge, complex 12 represents the first example of benzo-oxacycloheptylidene transition-metal complexes.…”

trans-Bis[bis(diphenylphosphino)methane-κ2P,P′]dichlororuthenium(II) dichloromethane disolvate acetone hemisolvate hemihydrate

“…The trans chloride geometry was proved by spectroscopic techniques only, namely 31 P NMR in solution. Four single-crystal structures containing the complex [RuCl 2 (dppm) 2 ] have been published; while three of them contain the cis isomer -the first as the non-solvated form (Chakravarty et al, 1984), the second cocrystallized with the fac-[RuCl 3 (dppm)(NO)] complex (Batista et al, 1999) and the third as a methanol solvate (Keller et al, 2003) -only one has a non-solvated trans configuration (Chakravarty et al, 1984). Four single-crystal structures containing the complex [RuCl 2 (dppm) 2 ] have been published; while three of them contain the cis isomer -the first as the non-solvated form (Chakravarty et al, 1984), the second cocrystallized with the fac-[RuCl 3 (dppm)(NO)] complex (Batista et al, 1999) and the third as a methanol solvate (Keller et al, 2003) -only one has a non-solvated trans configuration (Chakravarty et al, 1984).…”