Streamlined Preparation and Coordination Chemistry of Hybrid Phosphine–Phosphaalkene Ligands
dataset
posted on 2016-03-16, 20:13 authored by Kevin
W. Magnuson, Shelly M. Oshiro, Joshua R. Gurr, Wesley Y. Yoshida, Milan Gembicky, Arnold L. Rheingold, Russell P. Hughes, Matthew F. CainA 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>CHPMes*, 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>CHPMes*) 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>CHPMes*)Cl<sub>2</sub> (<b>2a</b>), Pd(Ph<sub>2</sub>PCH<sub>2</sub>CHPMes*)Cl<sub>2</sub> (<b>2b</b>), Pt(Cy<sub>2</sub>PCH<sub>2</sub>CHPMes*)Cl<sub>2</sub> (<b>3a</b>), and Pt(Ph<sub>2</sub>PCH<sub>2</sub>CHPMes*)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 PC 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 PC
double bond.
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