15-1 Predict the following products:

Mn2(CO)10 + Br2 → 2Mn(CO)5Br

HCCl3 + excess [Co(CO)4]- →
Co2(CO)8 + (SCN)2 → 2NCSCo(CO)4
Co2(CO)8 + (C6H5)CC(C6H5) (product has single Co-Co bond)
Mn2(CO)10 + [(η5- C5H5)Fe(CO)2]2 → (CO)5Mn-Fe(h5-C5H5) (CO)2

R
H

C
C

OC C CO
Co
Co Co
Co Co R CO
OC
CO OC
15-2 Find organic fragments that are isolobal with
Tc(CO)5
[Re(CO)4]-
[Co(CN)5]3-
[CpFe(η6- C6H6)]+
[Mn(CO)5]+
Os2(CO)8 (find organic molecule isolobal with dimeric molecule)

Tc(CO)5 -> 18-7-10 = 1 => CH3

[Re(CO)4]- -> 18-7-8-1 = 2 => CH2
[Co(CN)5]3- -> 18-9-5-3 = 1 => CH3
[CpFe(η6- C6H6)]+ -> 18-5-8-6+1=0 => CH4
[Mn(CO)5]+ -> 18-7-10+1 = 2 => CH3+
Os2(CO)8 (find organic molecule isolobal with dimeric molecule)
-> 18-8-8 = 2 >>> 2 M-M bond => H2C=CH2
15-3 Propose two organometallic fragments not mentioned in this chapter that are
isolobal with
CH3
CH
CH3+
CH3-
(η5- C5H5)Fe(CO)2
Sn(CH3)2

CH3 → L5M → M = d7
CH → L3M → M = d9
CH3+ → L5M → M = d6
CH3- → L5M → M = d8
(η5- C5H5)Fe(CO)2 → L5M → M = d7
Sn(CH3)2 → L4M → M = d8
15-4 Propose an organometallic molecule that is isolobal with each of the following:
Ethylene
P4 H H CO COCO
Cyclobutane
OC
C C OC Fe Fe CO
S8
H H CO CO
P P = 5
M
>>> L3M
P >>> 18-6-3 =9
M
P P >>> M = d9 M M

H H H CH2 >>> 6
C C >>> L4M M M
H H
C C >>> 18-8-2 =8
M M
H H H >>> M = d8

S >>> 6
S S S >>> L4M
M M M M
S S S >>> 18-8-2 =8
M M
S S >>> M = d8 M M
15-5 Hydrides such as NaBH4 and LiAlH4 have been reacted with the complexes
[(C5Me5)Fe(C6H6)]+, [(C5Me5)Fe(CO)3]+, and [(C5Me5)Fe(CO)2(PPh3)]+.
a. Show that these complexes are isolobal.
b. Predict the products of the reactions of these complexes with hydride reagents.

Fe H- Fe

H
H

H-
Fe Fe
OC CO OC CO
CO C
O H

H-
Fe Fe
Ph3P CO Ph3P CO
CO C
O H
15-6 Hoffmann has described the following molecules to be composed of isolobal
fragments. Subdivide the molecules into fragments, and show that the fragments
are isolobal.
a CO CO
OC H OC R
Fe C Mn P
OC H OC R
CO CO
b
CO CO
OC CO CO
Fe Fe Rh Rh
OC CO
CO CO OC

c
(CO)4 (CO)4
Re Re
(CO)4Re Re (CO)4 C C
Re Re
(CO)4 (CO)4
15-7 Verify that the following compounds are composed of isolobal fragments:
15-8 Calculations reported on the fragments Mn(CO)5, Mn(CO)3, Cu(PH3), and Au(PH3)
have shown that the energies of their singly occupied hybrid orbitals are in the
order Au(PH3) ＞ Cu(PH3) ＞ Mn(CO)3 ＞ Mn(CO)5
a. In the compound (OC)5Mn－Au(PH3), would you expect the electrons in the Mn
－Au bond to be polarized toward Mn or Au? Why? [Hint: Sketch an energy-level
diagram for the molecular orbital formed between Mn and Au.]
b. The Cu(PPh3) fragment bonds to C5H5 in a manner similar to the isolobal
Mn(CO)3 fragment. However, the geometry of the corresponding Au(PPh3) complex
is significantly different:
Suggest an explanation.
15-9 a. A tin atom can bridge two Fe2(CO)8 groups in a structure similar to that of
spiropentane. Show that these two molecules are composed of isolobal fragments.

(OC)4Fe Fe(CO)4 CH2

H2C
Sn C
(OC)4Fe H2C
Fe(CO)4 CH2

b. Tin can also bridge two Co(CO)(η5-C5Me5) fragments; the compound formed has
Co－Sn－Co arranged linearly. Explain the linear arrangement. (Hint: Find a
hydrocarbon isolobal with this compound.)
15-10 The AuPPh3 fragment is isolobal with the hydrogen atom. Furthermore, analogues
of the unstable CH5+, CH62+, CH73+ ions can be prepared using AuPPh3 analogues
of these ions and suggest a reason for their stability.
15-11 The C2 unit can form bridges between transition metals. For example, (CO)5
Mn(μ2-C2)Mn(CO)5 has been reported.
a. Show how two Mn(CO)5 fragments can interact in a σ fashion with bridging C2
ligand.
b. Show how π interactions can occur between C2 and the Mn(CO)5 fragments,
with the Mn(CO)5, using orbitals not involved in the σ interactions.
Mn C C Mn
dz2 dz2
3g

Mn C C Mn

1g
dxz, dyz dxz, dyz
15-12 The complex Mo2(NMe2)6 (Me = methyl) contains a metal-metal triple bond. Would
you predict this molecule to be more likely eclipsed or staggered? Explain.
15-13 In [Re2Cl8]2-, the dx2-y2 orbitals of rhenium interact strongly with the ligands. For
one ReCl4 unit in this ion, sketch the four group orbitals of the chloride ligand
(assume one σ donor orbital per Cl). Identify the group orbital of suitable
symmetry to interact with the dx2-y2 orbital of rhenium.
15-14 [Tc2Cl8]2- has a higher bond order than [Tc2Cl8]3-; however, the Tc－Tc bond
distance in [Tc2Cl8]2- is longer. Suggest an explanation.

[Tc2Cl8]2- : Tc3+ - Tc3+

[Tc2Cl8]3- : Tc3+ - Tc2+

15-15 Formal bond orders can sometimes be misleading. For example, [Re2Cl9]-, which
has a metal-metal bond order of 3.0, has a longer Re－Re bond (270.4 pm) than
[Re2Cl9]2- (247.3 pm), which has a bond order of 2.5. Account for the shorter bond
in [Re2Cl9]2-.

M-M repulsion + d orbitals expand

15-16 The molybdenum compounds [Mo2(DTolF)3]2(μ-OH)2, 1, and [Mo2(DTolF)3]2(μ-O)2,
2, have similar core structures, shown below (DTolF = [(p-tolyl)NC(H)N(p-tolyl)]-).
The molybdenum-molybdenum distance in 2 (214.0 pm) is slightly greater than
the comparable distance in 1 (210.7 pm). Suggest an explanation for this
difference.

1 2
+2 for per Mo
+2.5 for per Mo
↓
↓
d4
d3.5
15-17 Using the coordinate system of Figure 15-11, for B6H62-,
Show that the pz orbitals of the borons collectively have the same symmetry as
the s orbitals (generate a representation based on the six pz orbitals of the borons,
and do the same for the six pz orbitals).
Show that these representations reduce to A1g+Eg+T1u.
Show that the px and py orbitals of the borons form molecular orbitals of T2g and
T1u symmetry.
 6 0 0 2 2 0 0 0 4 2
A1g 1 1 1 1 1 1 1 1 1 1
T1u 3 0 -1 1 -1 -3 -1 0 1 1
Eg 2 -1 0 0 2 2 0 -1 2 0
 12 0 0 0 -4 0 0 0 0 0
T1g 3 0 -1 1 -1 3 1 0 -1 -1
T1u 3 0 -1 1 -1 -3 -1 0 1 1
T2g 3 0 1 -1 -1 3 -1 0 -1 1
T2u 3 0 1 -1 -1 -3 1 0 1 -1
15-18 For the closo cluster B7H72-, which has D5h symmetry, verify that there are 8
framework bonding electron pairs.

7 B => 28 valence atomic orbitals of B combine to form:

↓
n+1 bonding orbitals = 8 n B-H bonding orbitals 13 nonbonding orbitals
↓
8 framework MOs
1 bonding orbital from overlap of sp orbital
7 bonding orbitals from overlap of p orbital of B with sp hybrid orbitals
or p orbitals of other B orbitals
15-19 Classify the following as closo, nido, or arachno:
a. C2B3H7
b. B6H12
c. B11H112-
d. C3B5H7
e. CB10H13-
f. B10H142-

a. C2B3H7 => B5H9 => B5H54- => nido

b. B6H12 => B6H66- => arachno

c. B11H112- => closo

d. C3B5H7 => B8H10 => B8H82- => closo

e. CB10H13- => B11H14- => B11H114- => nido

f. B10H142- => B10H106- => arachno

15-20 Classify the following as closo, nido, or arachno:
a. SB10H102-
b. NCB10H11
c. SiC2B4H10
d. As2C2B7H9
e. PCB9H11-

a. SB10H102- => B11H132- => B11H114- => nido

b. NCB10H11 => B12H14 => B12H122- => closo

c. SiC2B4H10 => B7H13 => B7H76- => arachno

d. As2C2B7H9 => B11H15 => B11H114- => nido

e. PCB9H11- => B11H14- => B11H114- => nido

15-21 Classify the following as closo or nido:
a. B3H8Mn(CO)3
b. B4H6(CoCp)2
c. C2B7H11CoCp
d. B5H10FeCp
e. C2B9H11Ru(CO)3

a. B3H8Mn(CO)3 => B4H8 => B4H44- => nido

b. B4H6(CoCp)2 => B6H8 => B6H62- => closo

c. C2B7H11CoCp => B10H14 => B10H10-4 => nido

d. B5H10FeCp => B6H11+ => B6H6-4 => nido

e. C2B9H11Ru(CO)3 => B12H14 => B12H122- => closo

 15-22 Classify the following as closo, nido, or arachno:
a. Ge94-
b. InBi32-
c. Bi82+

a. Ge94- => 4 x 9 +4 = 40 valence electrons => 4n +4 => nido

b. InBi32- => 3 + 5 x 3 + 2 = 20 valence electrons = 4n +4 => nido

c. Bi82+ => 5 x 8 – 2 = 38 => 4n + 6 => arachno

The electrons offered from every apex are v + x – 12

v : The valence electrons of metal
x : The electrons offered from ligands
Structural type Skeletal electron:
Closo 2 (n+1)
Nido 2 (n+2)
Arachno 2 (n+3)
Hypho 2 (n+4)
15-23 Determine the number of skeketal electron pairs predicted by the mno rule for the
following:
a. arachno-B5H11
b. 1-(η5-C5H5)CoB4H10 (see Figure 15-16)
c. (η5-C5H5)Fe(η5-C2B9H11) (see Figure 15-19)

a. arachno-B5H11 => m = 1 => 8 skeletal electron pair

n=5
o=0
p=2

b. 1-(η5-C5H5)CoB4H10 (see Figure 15-16)

=> m = 2 => 15 skeletal electron pair
n = 10
o=1
p=2

c. (η5-C5H5)Fe(η5-C2B9H11) (see Figure 15-19)

=> m = 2 => 21 skeletal electron pair
n = 17
o=1
p=1
15-24 The ligand P5- has been reported to act as a stronger acceptor thanη5-C5H5-
a. Using the group orbital approach as for ferrocene (see Figure 13-27), sketch the
group orbitals arising from the P5 rings. Then show how the group orbitals can
interact with appropriate orbitals on a central transition metal.
b. On the basis of your diagram, suggest why the P5- ligand might act as a stronger
acceptor than η5-C5H5-.

s dz2 pz px py

a1g a2u e1u e1u

dxz dyz dxy dx2-y2

e1g e1g e2g e2g