Cyclopentadienyl-ruthenium and-Osmium Chemistry. IX. Some Substituted η1-Vinylidene and η1-Acetylide Complexes

Abstract

Reactions between RUCI(PPh3)2(η-C5H5), RuCI(L2)(η-C5H5)(L2 = dppm or dppe) or OsBr(PPh3)2-(η-C5H5) and the alk-1-ynes HC2R (R = Me, Pr, CO2Me, Ph, C6H4F-p or C6F5), in the presence of NH4PF6, NH4BF4 or NaBPh4, have given the corresponding cationic η1-vinylidene complexes [Ru(C=CHR)(PPh3)2(η-C5H5)]+,[Ru(C=CHPh)(L2)(η-C5H5)]+ or [Os(C=CHP~)(PPh3)2(η-C5H5)]+. These cations are readily deprotonated to give the corresponding η1-ethynyl derivatives Ru(C2R)-(PPh3)2(η-C5H5), Ru(C2Ph)(L2)(η-C5H5) or OS(C2Ph)(PPh3)2(η-C5H5). Addition of HPF6 or [R'3O]PF6 (R' = Me or Et) to the latter affords the vinylidene complexes containing C=CHR and C=CRR' ligands (R = Me, Pr, CO2Me, Ph, C6H4F-p or C6F5; R' = Me or Et), respectively. The vinylidene complexes are characterized by ν(CC) bands at c. 1650 cm-1 and the metal-bonded carbon (13C) resonance at c. 360 ppm.

Alkynyl compounds and nonlinear optics

“…Alkynyl complexes with a 4-nitrophenyl group at the alkynyl ligand can be considered to have a similar composition to efficient organics, but one in which the donor group is a ligated metal; the possibility of modifying the ligand environment at the metal affords the attractive prospect of a tunable donor group. The suite of complexes that we studied (Scheme 1) was readily accessed by extending literature procedures that had been developed for the synthesis of the related phenylalkynyl examples by Michael Bruce [14][15][16].…”

Neopentane-Based Tripodal CpL2 Ligands: Synthesis and Reactions of CH3C(CH2-η5-C5H4)(CH2-η1-PPh2)2RuCl; Hindered Rotation of Vinylidene Ligands

“…tion well-established in CpL 2 Ru chemistry. [30] The triflate salts of 7d/e are obtained as microcrystalline solids (7d or-If the appearance of two 31 P-NMR signals for 7b/c at low temperatures were to stem from a differentiation of the sur-ange-red, 7e brick-red). Their analytical and spectroscopic data (Table 12), as well as an X-ray analysis of 7e (Figure roundings of the two phosphorus nuclei by a helical twist of the chelate scaffolding Ϫ which would be dynamic at 3; Tables 4, 6, and 7) leave no doubt as to their constitutions.…”

Intermolecular Dehydrative Coupling and Intramolecular Cyclization of Ruthenium Vinylidene Complexes Formed from Aromatic Propynes Containing Carbonyl Functionalities

“…Electrospray ionization mass spectrometry,e lemental analyses and X-ray diffraction studies were carried out at the Regional Center of Analytical Instrument located at National Ta iwan University.T he ruthenium complex Cp(PPh 3 ) 2 RuCl [30] and compound 1a-1q [19] were prepared by following the method reported in the literature. All reagents were obtained from commercial suppliers and were used without further purification.…”