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and z characters in a way that reduces the antibonding between the metal and
surrounding ligands. The origin of this hybridization in a
1
is not much different from
that in the variation of cis and trans LML angles in ML
6
(Section 15.3). We shall
outline one way to viewthe resultant hybridization. The O
h
ML
6
to C
4v
ML
5
conversion
involves a reduction of symmetry. The 2a
1g
orbital (see Figure 15.1) and the z
component of 2t
1u
lie close in energy to 2e
g
. Both orbitals also will have a
1
symmetry
upon loss of the CO ligand. Consequently, they mix into the z
2
component of 2e
g
,
17.11 (in rst order), in a way that reduces the antibonding between the metal and its
surrounding ligands. Recall that 2a
1g
and2t
1u
lieat higher energy than2e
g
; thus, they mix
into 17.11 in a bonding manner. This is diagrammed in 17.12. Notice that it is the
phase relationship shown for the metal s and z in 17.12 to the ligand lone pairs in
17.11 that sets the mixing sign. 2a
1g
and 2t
1u
are, after all, concentrated at the metal.
Therefore, the largest interorbital overlap will occur between the atomic compo-
nents of 17.12 at the metal and the lone pairs in 17.11. The resultant orbital, 17.13,
is stabilized further by this mixing process, and it becomes hybridized out away from
the remaining ligands, toward the missing one. The a
1
orbital is empty for a d
6
fragment. It obviously will play a crucial role when real molecules are constructed
from the ML
5
fragment. Its directionality and the fact that it lies at moderate energy
make it a superlative s-accepting orbital. An MO plot at the extended Huckel level
of this orbital in Cr(CO)
5
is shown at the top of Figure 17.2. Notice the
distinct hybridization out toward the missing carbonyl. Returning to Figure 17.1,
FIGURE 17.1
Orbital correlation diagram for
the octahedrontosquare pyramid
conversion. Only the d orbital part
of the diagramis shown. Note the
rehybridization of z
2
toward the
empty coordination site.
17.2 THE C
4V
ML
5
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that is analogous to the a1 hybrid in the C4v ML5 fragment (Section 17.2). The
resultant orbital, 18.4, is labeled 2a1 in Figure 18.1. The 2a1g (z
2
) level will also be
stabilized very slightly by removing one ligand. The reader should note that we have
labeled each orbital in the ML3 fragment according to the C2v point group. We want
to emphasize, however, that one antibonding orbital is shifted to moderate energy
and it becomes hybridized out toward the missing ligand. The rest of the levels
remain basically unchanged, just as we saw for the square pyramidal ML5 fragment.
We have also included the z atomic orbital (AO), 2b2 in this gure. Occasionally this
orbital will be utilized (just as it is in square planar complexes). However, it must be
remembered that this orbital lies at a much higher energy than the others. Contour
plots of the important valence orbitals in PtCl3

are presented in Figure 18.2. In this

case the Cl

ligands are p donors. Therefore, their p AOs interact with the d AOs on
Pt in an antibonding way. This is particularly clear for the 1a2, 1b2, and 1b1molecular
orbitals. Note that even in the 2a1 orbital which is strongly s antibonding, there is still
noticeable p antibonding.
FIGURE 18.1
Construction of the orbitals of a
C2v ML3 fragment from a square
planar complex. The L ligands
contain only s donor hybrids.
504 18 THE C2v ML3 FRAGMENT
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E.6F16G .H I71:7J: K342
is stabilized by ethylene p

. The amount of forward and back donation in 18.48 and

18.49 is not expected to be precisely the same in both complexes. We can say with
some certainty that both effects will be important [36]. Computationally, this is a
quantity which is difcult to pin down. It is sensitive to the method, parameters (basis
set, and so on), and the exact details for partitioning electron density between the
atoms. What we can do is to establish trends. If p acceptor groups are substituted on
the ethylene, then the energies of p and p

drop. This makes the 18.49 (b

2
p

or
e p

) interaction stronger since the energy gap between the fragment orbitals
becomes smaller. The 18.48 interaction (a
1
p) must necessarily become smaller at
the same time since the energy gap between a
1
and p is larger. On the other hand
substitution of p donors on the ethylene ligand causes 18.48 to become stronger
and 18.49 weaker. With early transition metals the lled d AOs will be high in energy
so the 18.49 component becomes more important at the expense of 18.48. Late
transition metals will have the converse situation.
Returning to Figure 18.8 notice that if the ethylene were rotated by 90

so that it
lies in the PtCl
3
plane, the interaction between p and 2a
1
remains the same. The 2a
1
fragment orbital is cylindrically symmetric. Now p

interacts with b
1
rather than b
2
.
The overlap of the two metal orbitals with p

is similar. The same situation applies to

(ethylene)Cr(CO)
5
. Rotation of ethylene by 45

causes p

to interact with a
combination of the two members of the e set. However, in both cases the p orbital
interacts with a lled metal orbital [36] upon rotation. Therefore, the most stabile
orientations are those shown in Figure 18.8.
The analogy between the C
2v
ML
3
and C
4v
ML
4
fragments can be carried much
further. For example, the electronic features of the olen insertion reaction [37,38],
18.5018.51, in d
8
complexes are very similar to the catalytic olen hydrogenation
step for18.5218.53 for d
6
molecules [38,39]. The olen insertion reaction is
FIGURE 18.8
Orbital interaction diagrams
for two olenmetal
complexes.
18.4 COMPARISON OF C
2v
ML
3
AND C
4v
ML
5
FRAGMENTS 521
group that forms the s and s

MOs. To be fair the 1a

1
Cl
3
Pt

fragment orbital
is destabilized slightly by the methyl lone-pair, but this is a minor effect (for
overlap reasons) and the other three orbitals on Cl
3
Pt

are left rigorously non-

bonding. A number of d
9
d
9
M
2
L
6
dimers exist; 18.45 is one such example [33] and
Pt
2
(CO)
2
Cl
4
2
is another [34]. Each metal atom achieves a 16-electron count by the
formation of a metalmetal single bond. It is a straightforward matter to build up the
MOs of 18.45 from the union of two d
9
ML
3
fragments. The 2a
1
hybrids form
bonding (s) and antibonding (s

) molecular orbitals. 18.46 shows the orbital that

houses the two electrons from each singly occupied 2a
1
fragment orbital. There will
also be eight closely spaced MOs which are lled. They are derived from the in-phase
and out-of-phase combinations of 1a
1
, b
1
, a
2
, and b
2
orbitals of the ML
3
unit. The
separation between bonding and antibonding partners will depend on the metal
metal separation. This distance is fairly large for the PdPd single bond in 18.45 and
the splitting is therefore small. The orbital pattern is not at all different from that
derived for Re
2
(CO)
10
(see Section 17.4). The s bond, 18.47, has an obvious
resemblance to 18.46 for the M
2
L
6
dimers.
The left side of Figure 18.8 builds up the molecular orbitals for Zeises salt,
ethylene-PtCl
3

. The ethylene p level is stabilized by the 2a

1
acceptor orbital. One
member of the group of nonbonding metal functions, namely the b
2
level, has the
right symmetry to nd a match with ethylene p

. Consequently, the metal b

2
orbital
is also stabilized. This is the essence of the DewarChattDuncanson model [35] for
metalolen bonding. Charge from the lled ethylene p orbital is transferred to an
empty metal hybrid orbital, 18.48. There is also a backbonding component; charge is
transmitted from a lled metal d function to the empty ethylene p

orbital. This
pattern is also readily apparent for ethylene-Cr(CO)
5
on the right side of Figure 18.8.
The ethylene p orbital is stabilized by a
1
on Cr(CO)
5
and one component of the e set
520 18 THE C
2v
ML
3
FRAGMENT
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