90860-67-6Relevant academic research and scientific papers
RAPID INTRAMOLECULAR INTERACTIONS BETWEEN ORGANIC ISOCYANATES AND HEXAFLUOROBUT-2-YNE ON A DIRHODIUM CENTRE; X-RAY CRYSTAL STRUCTURE OF (η-C5H5)2Rh22(η3-C(CF3)C(CF3)C(O)N(Ph)>
Dickson, Ron S.,Nesbit, Rhonda J.,Pateras, Helen,Patrick, Jennifer M.,White, Allan H.
, p. C25 - C28 (1984)
Complexes of formula (η-C5H5)2Rh2 have been prepared by three methods, from reactions between organic isocyanates and (η-C5H5)2Rh2(CO)(CF3C2CF3) or (η-C5H5)2Rh2(CO)2(CF3C2CF3); by trteatment of (η-C5H5)2Rh2(CO)(CF3C2CF3) with organic azides; and by oxidation with Me3NO of the organic isocyanide in (η-C5H5)2Rh2(CO)(CNR)(CF3C2CF3).The crystal and molecular structure of the complex (η-C5H5)2Rh2 with R = Ph has been determined from single crystal X-ray diffraction data.This reveals that the isocyanate has condensed with the hexafluorobut-2-yne to form an amide ligand of the form C(CF3)C(CF3)C(=O)N(R); this bridges the two rhodium atoms in a μ2η3-manner.
The addition of small molecules to (η-C5H5)2Rh2(CO)(CF 3C2CF3). 3. The formation of a bridging acrylamide ligand on a dirhodium center by the cycloaddition of nitrenes, carbon monoxide, and an alkyne. X-ray crystal structure of (η-C5H5)2Rh ...
Dickson, Ron S.,Nesbit, Rhonda J.,Pateras, Helen,Baimbridge, Wayne,Patrick, Jennifer M.,White, Allan H.
, p. 2128 - 2134 (2008/10/08)
Full title: The addition of small molecules to (η-C5H5)2Rh2(CO)(CF 3C2CF3). 3. The formation of a bridging acrylamide ligand on a dirhodium center by the cycloaddition of nitrenes, carbon monoxide, and an alkyne. X-ray crystal structure of (η-C5H5)2Rh2[μ-η 3-C(CF3)C(CF3)C(O)N(Ph)]. Treatment of (η-C5H5)2Rh 2(μ-CO)(μ-CF3C2CF3) (1) with organic azides (N3R) in diethyl ether at 0°C results in the immediate formation of the complexes (η-C5H5)2Rh2[C(CF 3)C(CF3)C(O)N(R)] (2, R = Ph, PhCO, p-MeOC6H4SO2, (MeO2C)CH=C(CO2Me)). The related complexes 2 (R = i-Pr, Cy) are formed, together with the isocyanide complexes (η-C5H5)2Rh2(CO)(CNR)(CF 3C2CF3) (3), when 1 is treated with the appropriate carbodiimide (RNCNR) in dichloromethane at room temperature. Another route to the complexes 2 involves the addition of organic isocyanates to 1; this has been achieved with RNCO (R = Me, t-Bu, p-MeC6H4) at 70-80°C for several days. Finally, the complex 2 (R = t-Bu) is obtained by the oxidation with trimethylamine N-oxide of the isocyanide complex (η-C5H5)2Rh 2(CO)(CN-t-Bu)(CF3C2CF3). Determination of the crystal and molecular structure of the complex 2 (R = Ph) reveals that the bridging group is a substituted acrylamide of the form -C(CF3)=C(CF3)C(=O)N(Ph)-. Crystal data: C21H15F6NORh2, Mr = 617.2, tetragonal I41/a, a = 24.49(1) A?, c = 14.298 (4) A?, Z = 16, final R = 0.046, for 2559 observed reflections.
