72. Deegan, M. M.; Muldoon, J. A.; Hughes,
R. P.; Glueck, D. S.; Rheingold, A. L. Organometallics2018, 37, 1473-1482. Synthesis and Structure
of Metal Complexes of P-Stereogenic Chiral Phosphiranes: An
EDA-NOCV Analysis of the Donor–Acceptor Properties of
Phosphirane Ligands.
Abstract
Reaction of the enantiomerically enriched P-stereogenic
phosphiranes syn-(RP,SC)-Mes*PCH2CH(Ph)
(syn-1) and anti-(SP,SC)-Mes*PCH2CH(Ph)
(anti-2, Mes* = 2,4,6-(t-Bu)3C6H2)
with metal complex precursors gave Au(L)(Cl) (L = 1 (3);
L = 2 (4)), trans-ML2Cl2
(L = 1, M = Pd (5), Pt (6)), Pd(η3-C3H5)(L)(Cl)
(L = 1 (7)), and trans-RhL2(CO)(Cl)
(L = 1 (8); L = 2 (9)); 3, 4,
7, and 9 were crystallographically characterized.
Phosphirane coordination resulted in shortening of the P–C bonds
and increased bond angles at P, consistent with rehybridization at
phosphorus. A comparison of complexes of phenylphosphirane and
phenyldimethylphosphine using IR spectra, coupled with DFT studies
using electronic decomposition analysis (EDA) and natural orbitals
for chemical valence (NOCV), indicated that phosphiranes are
slightly poorer σ-donors than the analogous phosphines and that
the π-acceptor properties of these ligands are similar. Pauli
repulsion, dispersion, and electrostatic attraction are also
important factors in determining the strength of these
metal–ligand interactions.
