Chapter 5.

[Mo(CO)4(N-N)] Laboratory Introduction

Statement of Problem.
As computational chemistry techniques are becoming widely used in the chemical
sciences, it is vital that students have exposure to this technology at the undergraduate
level. Synthesis and characterization techniques, however, must remain the mainstay of
the laboratory curriculum. The focus of the following chapters of this thesis is the
development of the synthesis and characterization, which is incorporated with molecular
modeling, to form the integrated experiment. A series of [Mo(CO)4(N-N)] complexes,
where N-N = bidentate nitrogen donor ligand, were chosen for this research because they
generally respond well to computational methods, they are amenable to various physical
measurements that can be compared to computational findings, and these properties can
be modulated by changing the N-N ligand. The complexes were characterized by
1
electronic absorption spectroscopy, cyclic voltammetry, and H NMR spectroscopy;
many of them are new.

Review of the Related Literature.

Molybdenum Carbonyl Complexes.
6
The properties of d metal carbonyl complexes have been thoroughly elucidated
within the last thirty years.71 In particular, the photochemical and thermal reactions of
6
these complexes have been of interest. The d Cr(0), Mo(0), and W(0) complexes are
often studied together. Although similar in electronic structure, with the exception of
complexes with π-acid ligands, the characteristics of chromium complexes are quite
different from those of molybdenum and tungsten.71 The Cr(0) carbonyl complexes,
however, are the most widely investigated.
The area of research most fundamental to this work is the synthesis and
6 6
characterization of d [Mo(CO)4(N-N)] complexes. Unlike other d metal carbonyl
complexes, the chemistry of the N-N complexes has been sparsely investigated. Work on
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these complexes began with the thermal synthesis of [Mo(CO)4(N-N)], where N-N = bpy
(or similar N-N), and subsequent investigations into their crystal structures.72-75 These
complexes were synthesized by reacting [Mo(CO)6] with excess N-N ligand in
deoxygenated toluene at reflux. Reaction times for the thermal synthesis of [Mo(CO)4(N-
N)] complexes vary between 1.5 to 2 hours.

∆
[Mo(CO)6] + N-N [Mo(CO)4(N-N)] + 2 CO (1)
toluene

Additional thermal syntheses of [Mo(CO)4(N-N)] systems are noted in refs 73-75.

Recently, most [Mo(CO)4(N-N)] complexes are prepared photochemically
(equation 2) rather than thermally (equation 1).76-86 [Mo(CO)4(N-N)] systems are
prepared by photolysis of [Mo(CO)6] with excess N-N ligand in deoxygenated solvent
(equation 2).80 Required photolysis times range from between 30 to 60 minutes, and
varies depending on the N-N ligand used.

hν
[Mo(CO)6] + N-N [Mo(CO)4(N-N)] + 2 CO (2)

Photochemical substitution is effective for the formation of [M(CO)4(diimine)]

complexes, where M = Cr, Mo, or W, including those shown in Table 5.1. In most cases,
these complexes have been characterized by electronic absorption spectroscopy and X-
ray crystallography; characterization by infrared and NMR spectroscopy is also present in
the literature.

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Table 5.1. Select [Mo(CO)4(N-N)] Complexes Previously Synthesized and Investigated
via Thermal and/or Photolytic Synthesis.

N-N Ligand
a,b
1,10-phenanthroline
a
4-methyl-1,10-phenanthroline
a
5-methyl-1,10-phenanthroline
a
5-phenyl-1,10-phenanthroline
a
5-chloro-1,10-phenanthroline
a
5-nitro-1,10-phenanthroline
a
2,2’-bipyridine
a
4,4’-diphenyl- 2,2’-bipyridine
a,c
1,4-di-tert-butyl-1,4-diazabutadiene (1,4-dab)
b
4,5-diazafluorene (daf)
b
1,8-diazabiphenylene
d
2,2’-dipyridylamine
e
ethylenediamine

a. reference 144
b. reference 82
c. reference 145
d. reference 95
e. reference 74

The mechanism of photochemical substitution of [Mo(CO)6] is stepwise.75,82

Electronic absorption spectral evidence showed that upon photolysis, a [Mo(CO)5(N-N)]
intermediate is formed (equation 3). This is followed by a thermal step, the loss of the
second CO ligand, and subsequent N-N ring closure with the molybdenum center
(equation 4).

[Mo(CO)6] + N-N hν [Mo(CO)5(N-N)] + CO (3)

∆
[Mo(CO)5(N-N)] [Mo(CO)4(N-N)] + CO (4)

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 The predominant form of characterization for [Mo(CO)4(N-N)] complexes is
electronic absorption spectroscopy. Absorption and emission spectra for a series of
[Mo(CO)4(N-N)] complexes as well as the corresponding tungsten systems revealed that
the lowest-lying excited state for all of the complexes in the series resulted from metal to
ligand charge transfer (MLCT).87 This MLCT energy is ordered Mo > W > Cr.87 For N-N
in [Mo(CO)4(N-N)], the ligand energy level is ordered 1,10-phen > bpy > 5-Me-1,10-
phen > 5-Cl-1,10-phen ≈ 5-Br-1,10-phen > 5-nitro-1,10-phen.87 The lowest energy
transition for the [Mo(CO)4(N-N)] complexes is assigned as an MLCT transition, and
exhibits a large degree of solvent dependence.77,80,87-89,90 The other charge transfer
transitions are assigned to metal-to-carbonyl CT. These exhibit almost no solvent
dependence.80,87

Table 5.2. Electronic Absorption Spectral Data for [Mo(CO)4(N-N)] Complexes, where
N-N is a Bidentate Nitrogen Donor Ligand, daf = 4,5-diazafluorene, and dab = 1,4-di-
tert-butyl-1,4-diazabutadiene.

Complex Solvent Absorption Maxima (nm)

a
[Mo(CO)4(1,10-phen)] methanol 336, 395, 460
b
[Mo(CO)4(4,7-Ph2-1,10-phen)] benzene 339, 395, 502
b
[Mo(CO)4(5-chloro-1,10-phen)] benzene 344, 395, 502
b
[Mo(CO)4(5-nitro-1,10-phen)] benzene 340, 390, 512
a
[Mo(CO)4(bpy)] methanol 350, 392, 460
b
[Mo(CO)4(4,4’-Ph2-bpy)] benzene 350, 388, 484
b
[Mo(CO)4(4,4’-Me2-bpy)] benzene 354, 388, 482
c
[Mo(CO)4(1,4-dab)] benzene 375, 532
c
[Mo(CO)4(daf)] benzene 388, 478

a. reference 80
b. reference 82
c. references 144, 145

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 Many of the physical properties of [Mo(CO)4(N-N)] and related Cr and Ru
complexes exhibit interesting correlations.91-95 The spectroscopic energy gap can be
correlated with the electrochemical energy gap for the [Mo(CO)4(bpz)] system using a
free-energy diagram and physical data.91,93 Eop was determined utilizing electronic
absorption spectroscopy data and was plotted versus the electrochemically obtained ∆E
(∆E = E1/2oxd – E1/2red).91 A plot of this data resulted in a linear correlation with a negative
slope. The resulting free-energy relationship of the spectroscopic and electrochemical
values is shown in equation 5.

Eop = [χI + nF∆E + ∆∆Gs + Q] + χo + ∆(sol) (5)

In equation 5, χo + ∆(sol) = total change in solvation free energy, χI = inner sphere

(vibrational) component, and χo = outer sphere (solvent) component.91 Although the
negative slope obtained in the correlation plot was unexpected, the resulting correlation
coefficient (0.98) was reasonable.91 The authors also concluded that the techniques
utilized seemed justified, but higher-quality and more extensive data sets were
necessary.91

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