A rationally designed and selective synthesis of hybrid phosphine–phosphaalkene ligands <i><b>E</b></i><b>-1a</b> (Cy<sub>2</sub>PCH<sub>2</sub>CHPMes*, Mes* = 2,4,6-tri-<i>tert</i>-butylphenyl) and <i><b>E</b></i><b>-1b</b> (Ph<sub>2</sub>PCH<sub>2</sub>CHPMes*) was developed using phospha-Wittig methodology. The new hybrid ligands <i><b>E</b></i><b>-1a</b> and <i><b>E</b></i><b>-1b</b> were used to prepare the Pd and Pt dichloride complexes Pd­(Cy<sub>2</sub>PCH<sub>2</sub>CHPMes*)­Cl<sub>2</sub> (<b>2a</b>), Pd­(Ph<sub>2</sub>PCH<sub>2</sub>CHPMes*)­Cl<sub>2</sub> (<b>2b</b>), Pt­(Cy<sub>2</sub>PCH<sub>2</sub>CHPMes*)­Cl<sub>2</sub> (<b>3a</b>), and Pt­(Ph<sub>2</sub>PCH<sub>2</sub>CHPMes*)­Cl<sub>2</sub> (<b>3b</b>). The crystal structures of <i><b>E</b></i><b>-1a</b>, <i><b>E</b></i><b>-1b</b>, <b>2a</b>·1.33CHCl<sub>3</sub>, <b>3a</b>·CH<sub>3</sub>CN, and <b>3b</b> were determined. DFT calculations (M06/LACV3P**) on <b>2a</b> revealed that the π* orbital located on the PC unit is low-lying and accessible. An NBO analysis concluded that the phosphaalkene ligand is a significantly poorer σ donor and a slightly better π acceptor than its tertiary phosphine counterpart, due to the presence of the PC double bond

Similar works

Full text

oaioai:figshare.com:artic...Last time updated on 2/12/2018

This paper was published in FigShare.

Having an issue?

Is data on this page outdated, violates copyrights or anything else? Report the problem now and we will take corresponding actions after reviewing your request.