DFT computations unraveled a new H2 activation mechanism used by Ru(ii) pincer complexes to catalyze the N-formylation of amines with CO2 and H2 in the absence of external additives.
The hydrogenation of phenyl-substituted CN, CN, CC, CC and CO functional groups catalyzed by PNP pincer amido M(NO)(CO)(PNP) and amino HM(NO)(CO)(PNHP) complexes [M = Cr, Mo and W; PNP = N(CH2CH2P(isopropyl)2)2] has been computed.
Chemical treatment of CoX<sub>2</sub><b><sup>. </sup></b>6H<sub>2</sub>O (X = Cl,
Br, I) with the potentially tridentate PNP pincer ligand 2,6-bis(di-<i>tert</i>-butylphosphinomethyl)pyridine in
1:1 molar ratio results in cobalt(II) halide-PNP pincer complexes. The effect
of the hydrated metal source on molecular structure and geometry of the
complexes was studied by single crystal X-ray diffraction analysis. The
complexes are neutral and the cobalt center adopts a penta-coordinate system
with potential atropisomerization. Within
the unit cell there are two distinct molecules per asymmetric unit. One of the
two phosphorus atoms in the PNP ligand was observed to be partially oxidized to
phosphinoxide. Disorder in the structure reflects a mixture of square pyramidal
and distorted tetrahedral geometry.
