The structures of Ru(C5H5)(C2C6H5)[P(6H5)3]2, I, and [Ru(C5H5)(CO)[P(C6H5)3]2][B(C6H5)4], II, have been determined by X-ray diffraction methods at -162 °C. Complex I crystallizes with four molecules in space group C2h5-P21/c of the monoclinic system in a cell dimensions: a = 11.256(2) Å, b = 17.139(3) Å, c = 22.084(4) Å, and β = 118.52(1)°. The structure has been refined to and R index on F2 of 0.046 for 6214 observations and 441 variables. The carbonyl cation, complex II, crystallizes in the monoclinic space group C2h5-P21/a, with four formula units in a cell of dimensions a = 26.413(6), b = 14.953(7), c = 12.747(3) Å, β = 96.40(1)°. The structure of II has been refined to an R index on F2 of 0.069 for 10,072 observations and 641 variables. In complexes I and II the central Ru atom is in a distorted octahedral environment, with the cyclopentadienyl ring assuming three coordination sites trans to the two phosphines and either the acetylide or the carbonyl ligand. The RuC(acetylido) distance in complex I is 2.016(3) Å while in complex II the RuC(carbonyl) distance is 1.869(2) Å. Examination of the structural data and comparison with other Ru(II) complexes suggest little if any metalligand dπ-pπ interaction in the metal alkynyl complex, whereas the carbonyl complex displays extensive π-bonding.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry