53556-74-4Relevant academic research and scientific papers
Propargyl complexes of ruthenium
Shuchart, Chris E.,Willis, Richard R.,Wojcicki, Andrew
, p. 185 - 198 (1992)
The first ruthenium-propargyl complexes CpL2RuCH2CCPh (L = CO (1) and PPh3 (2)) were synthesized by reaction of - with PhCCCH2Cl or PhCCCH2OS(O)2C6H4Me-p and of Cp(PPh3)2RuCl with PhCCCH2MgCl, respectively.In contrast, treatment of - with HCCCH2Cl affords the ruthenium-η1-allenyl complex Cp(CO)2RuCH=C=CH2 (3).Complex 1 is protonated by HBF4 * OEt2 to 2-CH2=C=CHPh)>BF4 (4a), which isomerizes within 2 h in acetone solution at room temperature to 2-CH2=C=CHPh)>BF4 (4b).Compound 4b reacts with Pt(PPh3)2(C2H4) to give the ruthenium-substituted platinum(II)-η3-allyl complex 3-CH2C(Ru(CO)2Cp)CHPh)Pt(PPh3)2>BF4 as the anti isomer quantitatively.Compound 1 undergoes facile cycloaddition reactions with tetracyanoethylene (TCNE) and p-toluenesulfonyl isocyanate (TSI); the latter reaction in CH2Cl2 solution at 25 deg C proceeds slightly more rapidly (1.3 times) than the corresponding reaction of Cp(CO)2FeCH2CCPh.With Co2(CO)8, 1 yields the trinuclear (CO)3Co(μ-η2-PhCCCH2Ru(CO)2Cp)Co(CO)3, which undergoes very slow cleavage of the Ru-CH2 bond with CF3CO2H, and replacement of CO (at Co) with PPh3.The foregoing reactions are compared and contrasted with the corresponding reactions of Cp(CO)2FeCH2CPh.Where a comparison has been made, 2 was found to react faster than 1; however, its chemistry tends to be complicated by the lower stability of products and a facile PPh3-CO ligand exchange.With TSI and Co2(CO)8, the products are analogous of those of 1, but with Fe2(CO)9, Cp(CO)(PPh3)RuCH2CCPh and Fe(CO)4PPh3 are obtained instead of heteronuclear metal complexes.
Pauson-Khand reactions in a photochemical flow microreactor
Asano, Keisuke,Uesugi, Yuki,Yoshida, Jun-Ichi
supporting information, p. 2398 - 2401 (2013/06/27)
Pauson-Khand reactions were achieved at ambient temperature without any additive using a photochemical flow microreactor. The efficiency of the reaction was better than that in a conventional batch reactor, and the reaction could be operated continuously for 1 h.
Reactions of transition-metal-propargyl compounds with dicobalt octacarbonyl. New heterobinuclear μ-alkyne complexes
Wido, Thomas M.,Young, George H.,Wojcicki, Andrew,Calligaris, Mario,Nardin, Giorgio
, p. 452 - 458 (2008/10/08)
Reactions of transition-metal-propargyl complexes [M]CH2C≡CR with Co2(CO)8 in pentane at room temperature afford the trinuclear products (CO)3Co(μ-RC2CH2[M]Co(CO)3 ([M] = CpFe(CO)2, R = Ph (1a), Me (1b); [M] = Mn(CO)5, R = Ph (2); [M] = CpW(CO)3, R = Ph (3a), Me (3b); [M] = CpMo(CO)3, R = Ph (4)) as purple solids of different degrees of stability (1a, 1b, and 2 ? 3a, 3b, and 4). Treatment of 1a and 2 with CF3CO2H and alumina, respectively, leads to cleavage of the M-CH2 bond with the formation of (CO)3Co(μ-PhC2Me)Co(CO)3 and CpFe(CO)2OC(O)CF3 (from 1a). By contrast, 3a, 3b, and 4 react with CF3CO2H and alumina surprisingly to give heterobinuclear μ-alkyne complexes, Cp(CO)2M(μ-RC2Me)Co(CO)3 (5a, 5b, and 6, respectively) as air-stable, red solids. Complexes 1-6 were characerized by a combination of elemental analyses, FAB mass spectrometry, and IR and 1H and 13C NMR spectroscopy; the structure of 5a was determined by single-crystal X-ray analysis. Crystal data: monoclinic, space group P21/n with a = 8.825 (2) A?, b = 15.003 (2) A?, c = 14.035 (2) A?, β = 93.42 (1)°, and Z = 4. The structure was solved and refined to R = 0.0249 and Rw = 0.0268 by using 3918 independent reflections. The alkyne PhC2Me is transversely bridging the Co-W bond (2.693 (1) A?), and its Me substituent is trans to Cp.
Preparation and molecular structure of a heterobimetallic acetylene complex, μ-C6H5C≡CC6H5H[(CO) 3Co-Ni(η5-C5H5)]
Freeland, Brian H.,Hux, Janet E.,Payne, Nicholas C.,Tyers, Kenneth G.
, p. 693 - 696 (2008/10/08)
The heterobimetallic acetylene complex μ-(diphenylacetylene)-(tricarbonylcobaltio)(η 5-cyclopentadienyl)nickel, (μ-C6H5C≡CC6H5)[(CO) 3Co-Ni(η5-C5H5)], has been separated from the reactions of (μ-C6H5C≡CC6H5)[Ni 2(η5-C5H5)2] with Co2(CO)8, (μ-C6H5C≡CC6H5)[Co 2(CO)6] with nickelocene, (μ-C6H5C≡CC6H5)[Co 2(CO)6] with (μ-C6H5C≡ CC6H5)[Ni2(η5-C 5H5)2] and (η5-C5H5)2Ni 2(CO)2, and diphenylacetylene with (η5-C5H5)NiCo3(CO)9. (μ-C6H5C≡ CCH3)[(CO)3Co-Ni(η5-C5H 5)] has been prepared in similar fashion. The compounds have been characterized by mass spectrometry, infrared spectroscopy, and NMR studies. A single-crystal X-ray structure determination of the diphenylacetylene compound shows the acetylene bonded perpendicularly to the metal-metal bond. Crystals are orthorhombic, of space group Pbca, with unit cell dimensions a = 15.799 (4), b = 21.460 (5), and c = 11.608 (3) A?, with Z = 8. Refinement on F, using 3062 unique diffractometer data, converged to a final agreement factor R = 0.040. The Ni-Co bond distance is 2.3656 (8) A?, and the acetylene is distorted significantly from linearity (mean deviation 40.1 (1)°).
