Syntheses and Structural Studies of Several Group 8 Metal Complexes Derived from 1, 3‐Butadiyne

Abstract

AbstractAs part of an extensive investigation into the chemistry of complexes containing metal‐ligand centers linked by chains of C(sp) atoms, the preparation, characterization, and single‐crystal X‐ray diffraction molecular structure determinations of four complexes {MLn}‐C≡CC≡C‐{M′L′m} [MLn = Ru(dppe)Cp*, M′L′m = Fe(dppp)Cp* (1), Ru(dppe)Cp* (2), MLn = M′L′m = Os(PPh3)2Cp (3)], and {Cp*(dppe)Ru}C≡CC≡C{trans‐RuCl(dppe)2} (4), in which the alternating C(sp)–C(sp) bonds have values between 1.375 and 1.40 Å (single) and between 1.20 and 1.259 Å (triple), respectively, are described. In addition, a structure determination of Ru3(μ‐H){μ3‐C2C≡C[Ru(PPh3)2Cp]}(CO)9 (5) shows that the C2 fragment attached to the HRu3 cluster shows the expected lengthening [to 1.311(7) Å] and bending at the two carbon atoms [to 152.6(6) and 157.6(5)°] (resulting from back‐bonding from the Ru3 cluster into the C≡C π* orbitals) compared with the essentially linear Ru–CC– moiety [C≡C 1.222(6) Å, angles at C of 178.0(5), 172.3(6)°],