ja306947m_si_004.cif (23.34 kB)
Exploiting the π‑Acceptor Properties of Carbene-Stabilized Phosphorus Centered Trications [L3P] 3+: Applications in Pt(II) Catalysis
dataset
posted on 2012-10-10, 00:00 authored by Javier Carreras, Mahendra Patil, Walter Thiel, Manuel AlcarazoReaction of tris(dimethylaminocyclopropenium) substituted
phosphine 1 with K2PtCl4 afforded
the bench stable
complex 3 which upon treatment with Ag[CB11H6Cl6] turned out to be an excellent catalyst
for the transformation of a variety of ortho-biaryl
substituted alkynes into polycyclic homo- and heteroarenes of different
size, shape, and curvature through a 6-endo-dig cyclization.
This constitutes the first example ever reported of using a P1-centered trication as ligand in catalysis. The strong π-acceptor
character of 1 that derives from its three positive charges
substantially increases the intrinsic π-acidity of Pt in complex 1·PtCl2 and dramatically enhances its ability
to activate π-systems toward nucleophilic attack. As a consequence,
a remarkable acceleration of the model transformation is observed
when compared with other classical π-acceptor ligands such as
P(OPh)3 or P(C6F5)3. Moreover,
the employment of 1 as ligand also expands the scope
of this reaction to previously inaccessible substitution patterns.
Kinetic studies and deuterium labeling experiments as well as density
functional theory (DFT) calculations were performed in order to explain
these findings.