268749-08-2Relevant academic research and scientific papers
16-Electron ruthenium(0) complexes containing the Ru(NO)L2+ substructure: Planar RuCH3(NO)L2 vs sawhorse [Ru(NO)(C=C(SiMe3)2)L2]+
Huang, Dejian,Streib, William E.,Eisenstein, Odile,Caulton, Kenneth G.
, p. 1967 - 1972 (2000)
The synthesis and characterization of RuCl(NO)L2 (L = PiPr3 and PtBu2Me) and RuX-(NO)L2 (X = F, CH3, OSO2CF3, and H) are reported. All are planar at Ru. Reaction of Ru-(OSO2CF3)(NO)L2 with NaBAr′4 (Ar′ = C6H3(CF3)2) in CH2Cl2 gives RuCl(CH2Cl)(NO)L2+, while in C6H5F in the presence of Me3SiC≡CSiMe3, the vinylidene complex Ru[C=C(SiMe3)2]-(NO)L2+ is formed. The latter is a sawhorse structure (i.e., P's trans but NO and C=C-(SiMe3)2 cis) and stands in contrast to the oxidative addition isomer Ru(CO)(SiMe3)(C≡ CSiMe3)L2 for the carbonyl analogue. The reason for the thermodynamic reversal for CO vs NO+ is discussed on the basis of DFT/(B3PW91) calculations, and the calculated structure shows bending of the nitrosyl, consistent with considerable back-donation.
