Symmetry of PolyoxometalateBased Late-Transition-MetalOxo Complexes And The “Oxo
Group Theory. December 4th, 2013
◦ The Oxo Wall
◦ The Vanadyl Ion (C4v)
Late transition metal M=O symmetries
◦ AuO (C2v)
◦ Pt-oxo and Pd-oxo (C4v)
Revisiting the late transition metal M=O
◦ The square planar Pd unit (D4h)
Terminally bound oxo species are
proposed as intermediates of
important catalyzed reactions.
The Oxo Wall:
◦ “M=O groups are stabilized at metal
centers with an oxidation state of no less
than 4+ and no more than four d
Groups 3-6 are stable
Groups 7-8 are more reactive
Groups 9-11 are rare (electrons begin
to populate antibonding orbitals)
s-orbitals transform as A1
p-orbitals transform as A1+E
d-orbitals transform as A1+B1+B2+E
1 1 3 1 = 2A1+B1+E
Transitions (E initial state)
◦ E (A1+E)=E + A1+A2+B1+B2
◦ All allowed transitions
Transitions (B2 initial state)
◦ B2 (A1+E)=E +B2
◦ Only pure electronic transitions to states
with E or B2 symmetry are allowed.
Group Theory can help us assign and
describe the symmetry of MOs.
We can assess the symmetry of
transitions even if we don’t know their
Group Theory can’t help us in
structure determinations, since it
requires us to postulate a structure
with a point group
C J Ballhausen et al, Inorg. Chem.
1962, 1(1), 111.
K P Halloran et al, Inorg. Chem.,
2012, 51 (13), 7025–7031.
T M Anderson et al, Science, 2012,
306, 2074 .
T M Anderson et al, J. Am. Chem.
Soc., 2005, 127, 11948.
R Cao et al, J. Am. Chem. Soc., 2007,