Ethinyl- und Butadiinylkomplexe des Eisens und Rutheniums mitterminalen Hauptgruppenelement-Substituenten, Cp * Fe(Ph 2PCH(X)CH 2PPh 2) C ≡ CY (X = H, PPh 2; Y = H, PPh 2, P (+)Ph 2Me) und Ru(Ph 2PCH 2PPh 2) 2(X) C ≡ CC ≡ CSiMe 3 (X = Cl, C ≡ CC ≡ CSiMe 3)

Abstract

Treatment of Cp * Fe(dppe)C ≡ CH (dppe = Ph 2PCH 2CH 2PPh 2), 1, with an equimolar quantity of t-BuLi or with 2.5 equivalents of MeLi, followed by addition of ClPPh 2, yielded Cp * Fe(dppe)C ≡ CPPh 2, 2. With excess t- or n-BuLi, the ethylene bridge of the dppe ligand in 1 was also metallated, and further reaction with ClPPh 2 resulted in Cp * Fe(tppe)C ≡ CPPh 2 (tppe = Ph 2PCH(PPh 2)CH 2PPh 2), 3. Quaternization of 3 by Mel smoothly produced the phosphoniumethynyl derivative [Cp * Fe(tppe)C ≡ CPPh 2me]I, 4. Reactions of cis-Ru(dppm) 2Cl 2 (dppm = Ph 2PCH 2PPh 2) with LiC ≡ CC ≡ CSiMe 3, in situ generated from Me 3SiC ≡ CC ≡ CSiMe 3 and MeLi/LiBr in THF, gave cis-Ru(dppm) 2(C ≡ CC ≡ CSiMe 3) 2, 5, trans-Ru(dppm) 2(C ≡ CC ≡ CSiMe 3) 2, 6, and trans-Ru(dppm) 2(Cl)C ≡ CC ≡ CSiMe 3, 7, depending on the solvent (ether or THF) and the molar ratios of the reactants. According to an X-ray structure analysis, the ethynyl ligand of 1 is structurally characterized by d(Fe-C), 1.876(13) and d(C ≡ C), 1.206(15) Å, the value of the angle Fe-C≡C being 176.3(11)°.