Abstract
A single-crystal X-ray study confirms that the reaction of IrH(CO)2(PPh3)2 (Ph = phenyl) with 2 mol of tetracyanoethylene (TCNE) yields (cyano(dicyanomethyl)keteniminato)carbonyl(tetracyanoethylene)bis(triphenylphosphine)iridium, Ir(C6N4H)(CO)(TCNE)(PPh3)2. The cyano(dicyanomethyl)keteniminato moiety is formed formally by hydrogen migration from the Ir to a TCNE molecule and subsequent attachment of the resulting group to the Ir through an Ir-N bond. The geometry about iridium is trigonal bipyramidal with the two phosphorus atoms and the olefinic 7r-bonded TCNE in the equatorial plane while the carbonyl and keteniminato groups occupy axial positions. The average Ir-P and coplanar Ir-C distances are 2.392 (7) and 2.166 (15) A, respectively. The Ir-N distance is 2.204 (8) Å and the Ir-N-C angle is 161.9 (7)°. The compound crystallizes in space group P21/c of the monoclinic system with four molecules of the iridium complex and two molecules of benzene in a cell of dimensions a = 13.012 (7), b = 16.099 (9), c = 21.740 (12) Å, β = 94.33 (2)°. The observed and calculated densities are 1.54 (1) and 1.52 g cm-3, respectively. The structure has been refined by least-squares techniques to a final R factor on F of 4.1 % based on 3853 observations above background.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 2391-2397 |
| Number of pages | 7 |
| Journal | Journal of the American Chemical Society |
| Volume | 93 |
| Issue number | 10 |
| DOIs | |
| State | Published - May 1 1971 |
ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry