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Abstract:
Multiple bonding in the terminal phosphido complex [Ru(PCy2)(η5-indenyl)(PPh3)] (2a) is clearly demonstrated by solution, solid-state, and computational studies. Reactions of this dark blue, half-sandwich complex with CO, MeI, HNEt3Cl, HCl, NH4PF6, H2, and Et3SiH demonstrate an unusual range of behavior resulting from combined coordinative unsaturation at Ru, high nucleophilicity/basicity of the phosphido P, and π-character of the Ru−P interaction. The terminal, π-bound phosphido structure is general for a range of PR2 species (R = Pri (2b), Ph (2c), Tolp (2d)). The very reactive diarylphosphido analogues 2c,d have been observed spectroscopically at low temperatures and can be trapped quantitatively as their CO adducts, [Ru(PAr2)(η5-indenyl)(CO)(PPh3)] (3c,d), in which the Ru−P bond order is reduced to 1. Complex 2a and its analogue [Ru(PPri2)(η5-indenyl)(PPh3)] (2b) are consistently isolated with ∼15% of their structural isomers, the ruthenium hydrido phosphaalkenes 9a,b, resulting from an apparent 1,2-H shift.
