| Autor: |
Huang, D., Streib, W. E., Eisenstein, O., Caulton, K. G. |
| Zdroj: |
Organometallics; May 2000, Vol. 19 Issue: 10 p1967-1972, 6p |
| Abstrakt: |
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 NaBAr4 (Ar = C6H3(CF3)2) in CH2Cl2 gives RuCl(CH2Cl)(NO)L2+, while in C6H5F in the presence of Me3SiC&tbd1;CSiMe3, the vinylidene complex Ru[C&dbd;C(SiMe3)2](NO)L2+ is formed. The latter is a sawhorse structure (i.e., P's trans but NO and C&dbd;C(SiMe3)2 cis) and stands in contrast to the oxidative addition isomer Ru(CO)(SiMe3)(C&tbd1;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. |
| Databáze: |
Supplemental Index |
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