Facile
Formation of Stable Tris(imido)phosphate Trianions
as Their Tri- and Hexanuclear Pd(II) Complexes in Protic Solvents
Arvind
K. Gupta
S. Arun Dixith Reddy
Ramamoorthy Boomishankar
10.1021/ic400686e.s002
https://acs.figshare.com/articles/dataset/Facile_Formation_of_Stable_Tris_imido_phosphate_Trianions_as_Their_Tri_and_Hexanuclear_Pd_II_Complexes_in_Protic_Solvents/2400868
Employing Pd(OAc)<sub>2</sub>, a
facile deprotonation route to
access the highly basic tris(alkylimido)phosphate trianions, [(RN)<sub>3</sub>PO]<sup>3–</sup> (R = <sup>t</sup>Bu, <sup>c</sup>Hex,
or <sup>i</sup>Pr), analogous to the orthophosphate (PO<sub>4</sub><sup>3–</sup>) ion in polar and in protic solvents has been
achieved. Trinuclear and prismatic Pd(II) clusters of these imido
trianions having the formula {Pd<sub>3</sub>[(NR)<sub>3</sub>PO](OAc)<sub>3</sub>}<sub><i>n</i></sub> (<i>n</i> = 1 or
2) or as mixed-bridged clusters of the type {Pd<sub>3</sub>[(N<sup>i</sup>Pr)<sub>3</sub>PO](OAc)<sub>2</sub>(<i>OR</i>′)}<sub>2</sub> (R′ = Me or H) were isolated exclusively in all these
reactions in which the trianionic species acts as a tripodal chelating
ligand to the trinuclear Pd<sub>3</sub> unit. Reactivity studies aiming
at the Pd(II) atoms in these clusters with nucleophilic reagents,
such as primary amines (R″NH<sub>2</sub>), have led to a new
trimeric cluster with the formula {Pd<sub>3</sub>[(NR)<sub>3</sub>PO](OAc)<sub>3</sub>(R″NH<sub>2</sub>)<sub>3</sub>} in which
the tripodal coordination of the Pd–N<sub>imido</sub> moieties
remained unaffected, exemplifying the robustness of the Pd<sub>3</sub> unit in all these clusters. We have also shown the catalytic activity
of these Pd(II) complexes in Mizoroki–Heck type coupling reactions
in the presence of Cu(OAc)<sub>2</sub>.
2016-02-19 04:47:10
trimeric cluster
RN
Pd 3 unit
tripodal chelating ligand
tripodal coordination
PO
nucleophilic reagents
protic solvents
Reactivity studies
Facile Formation
trinuclear Pd 3 unit
imido trianions
trianionic species acts
deprotonation route