155804-79-8Relevant academic research and scientific papers
Heteronuclear iron-ruthenium complexes containing bridging allenyl and allenylcarbonyl ligands
Shuchart, Chris E.,Wojcicki, Andrew,Calligaris, Mario,Faleschini, Paolo,Nardin, Giorgio
, p. 1999 - 2009 (1994)
Reactions of Cp(CO)2RuCH2C≡CPh (1) with Fe2(CO)9 yield one or more of the products (CO)3Fe(μ-η3:η2-C(O)C(Ph)=C=CH 2)Ru(CO)Cp (2), (CO)3Fe(μ2-CO)RuCp(μ2-CO)Fe(CO) 3(μ3-η1-CCH=CHPh) (3), (CO)3FeRu(CO)CpFe(CO)3(μ3-η 1:η1:η3-CCHCHPh) (4), (CO)3FeFe-(CO)3Ru(CO)Cp(μ3-η 1:η2:η2-C(Ph)=C=CH2) (5), and (CO)3FeFe(CO)3Ru(CO)Cp(μ3-η 1:η2:η2-CH=C=CHPh) (6), depending on solvent, relative amounts of the reactants, and reaction time and temperature. The novel binuclear metal μ-allenylcarbonyl complex 2 is best prepared in THF at 0°C, whereas the capped trinuclear metal clusters 3 and 4 are obtained, along with 2, in diethyl ether at reflux. The trinuclear metal μ3-η1:η2:η2-allenyl products 5 and 6 result from the reaction of 1 with a large excess of Fe2(CO)9 in hexane at reflux. In the formation of 3, 4, and 6, a methylene hydrogen shift occurs within the C3H2Ph ligand. Reaction of 1 with Ru3(CO)12 in hexane at reflux affords (CO)3RuRu(CO)3Ru(CO)Cp(μ3-η 1:η2:η2-C(Ph)=C=CH2) (7), which is structurally analogous to 5. Complex 2 undergoes monosubstitution at iron with each of PPh3 and Ph2PCH2PPh2 (dppm) at room temperature to yield 8 and 9, respectively. Thermolysis of (η1-dppm)(CO)2Fe(μ-η3:η 2-C(O)C(Ph)=C=CH2)Ru(CO)Cp (9) affords disubstituted, dppm-bridged (CO)2Fe(μ-η3:η2-C(O)C(Ph)=C=CH 2)(μ-dppm)RuCp (10). Reaction of 5 with PPh3 in hexane at reflux furnishes a monosubstitution product with Fe - PPh3 bonding. All complexes were characterized by a combination of elemental analysis, mass spectrometry, and IR and 1H, 13C, and 31P NMR spectroscopy. The structures of 2, 5, and 6 were determined by X-ray diffraction analysis. 2: monoclinic, P21/c, a = 7.037(5) A?, b = 17.20(1) A?, c = 29.69(2) A?, β = 95.58(5)°, Z = 8, R = 0.065, Rw = 0.074; 5: monoclinic, P21/c, a = 8.068(3) A?, b = 15.333(4) A?, c = 16.849(3) A?, β = 95.11(1)°, Z = 4, R = 0.037, Rw = 0.042; 6: monoclinic, P21/c, a = 8.999(4) A?, b = 12.914(6) A?, c = 36.15(1) A?, β = 93.46(2)°, Z = 8, R = 0.057, Rw = 0.075.
