49771-94-0Relevant academic research and scientific papers
Unusual isomerization of ortho-chelated aryliridium(I) complexes, involving a unique sequence of intramolecular C-H bond-making and -breaking processes. X-ray structure of IrI[C6H3(CH2NMe2) 2-2,4](COD)
Van Der Zeijden, Adolphus A. H.,Van Koten, Gerard,Luijk, Ronald,Nordemann, Richard A.,Spek, Anthony L.
, p. 1549 - 1556 (2008/10/08)
The reaction of Lin[C6H3(CH2NMe 2)-2-R-6]n with [IrCl(COD)]2 yields the ortho-chelated aryliridium(I) complexes Ir[C6H3(CH2NMe2)-2-R-6](COD) [R = CH2NMe2 (4), Me (5), H (6); COD = 1,5-cyclooctadiene]. In solution complexes 4 and 5 isomerize irreversibly at 60°C to Ir[C6H3(CH2NMe2)-2-R-4](COD) (7 and 8, respectively). The mechanism of this conversion involves the initial intramolecular oxidative addition of one of the NMe C-H bonds, succeeded by a unique sequence of highly regiospecific C-H bond-breaking and -making processes. The solid-state structure of 7 was determined by an X-ray diffraction study. Crystals are monoclinic of space group C2/c with Z = 8 and lattice parameters a = 23.829 (2) A?, b = 11.667 (2) A?, c = 13.725 (1) A?, and β = 93.43 (1)°. The structure was refined to R = 0.026 for 3087 observed reflections. The structure of 7 consists of an iridium(I) center that is square planar coordinated by the two double bonds of COD and by the monoanionic aryl ligand through an aromatic C atom and the N atom of the 2-CH2NMe2 group.
Synthesis of ortho deuterated phenylisocyanate under mild conditions
Masson,Dormoy
, p. 785 - 790 (2007/10/13)
A new method has been developed for the synthesis of phenylisocyanate 2-2H through the use of azido (tris dimethylamino) phosphonium hexafluorophosphate and benzoic acid 2-2H. The product prepared is obtained with a high percentage of isotopic substitution, specificity of label and appreciable yield.
