83399-40-0Relevant academic research and scientific papers
Bent nitrene ligands attached to rhenium. Syntheses and low-temperature structures of trans-Re(OC2H5)(p-NC6H4CH 3)(S2CN(CH3)2)2 and related compounds
Goeden, Gary V.,Haymore, Barry L.
, p. 157 - 167 (2008/10/08)
New rhenium nitrene complexes, Re(NR)(S2CNR′2)3 and Re(OR″)(NR)(S2CNR′2)2 (R = CH3, C6H5, p-CH3C6H4; R′ = CH3, C2H5; R″ = CH3, C2H5), have been prepared from ReCl(NR)(S2CNR′2)2 by the action of TlS2CNR′2, (CH3)3SiSC(S)NR′2, or NaOR″. Infrared and 1H NMR spectroscopic data suggest that (1) the tris(dithiocarbamate) complexes possess cis, six-coordinate geometries with one monodentate dithiocarbamate group and that (2) two trans isomers of the alkoxy complexes are present in solution. Brown solvent-free crystals of Re(OC2H5)(p-NC6H4CH 3)(S2CN(CH3)2)2 were grown from methylene chloride-ethanol. The structure of the complex was determined at -175°C with use of X-ray diffraction techniques. The complex is monomeric and six-coordinate and has a distorted, trans, octahedral geometry. The dithiocarbamate ligands have nearly identical structural parameters with S-Re-S bite angles of 71.97 (6) and 71.67 (6)°; the Re atom is 0.135 (3) A? out of the plane of the four sulfur atoms toward the nitrogen atom of the nitrene ligand. The nitrene ligand is significantly bent at the nitrogen atom (Re-N(3)-C(31) = 155.5 (5)°) with an abnormally long Re-N(3) distance of 1.745 (5) A?. The ethoxy ligand is also bent at the oxygen atom in the same plane as the nitrene with Re-O-C(41) = 131.7 (4)° and Re-O = 1.948 (4) A?. The title complex crystallizes in space group P21/c with a = 9.190 (3) A?, b = 17.459 (4) A?, c = 14.082 (4) A?, β = 116.90 (2)°, and Z = 4. On the basis of 3315 unique reflections with Fo2 > 3σ(Fo2), the structure was refined with use of full-matrix, least-squares methods to R(F) = 0.035 and Rw(F) = 0.043.
