Journal of the Less-Common Metals, 36(1974) 95 - 102 95

@ Elsevier Sequoia S.A., Lausanne - Printed in The Netherlands

MOLYBDENUM SPECIES IN AQUEOUS SOLUTION - A BRIEF

SUMMARY *

G. P. HAIGHT and DAVID R. BOSTON

School of Chemical Sciences, University of Illinois, Urbana, Ill. 61801 (U.S.A.)

SUMMARY

The aqueous solution chemistry of molybdenum in oxidation states (VI) to (II) is

reviewed with particular reference to (a) the structures of oxomolybdenum species,
(b) formation and properties of complexes, (c) redox behaviour, (d) molybdenum-
catalysed reactions.

INTRODUCTION

Complex ions of molybdenum in all oxidation states from (II) to (VI) are known to
exist in aqueous solution. Complexes of molybdenum(VI) and (V) in aqueous solutions
are of special interest due to the implication of Mo(V1) and (V) in some important enzy-
matic redox systems. Most such complexes are labile, potentials for changing oxidation
states are low, and the tendency to form 0- and S- bridged polynuclear complexes is
high. These properties make molybdenum a versatile site for reactions and catalyses in
biochemical systems, but they also make clear cut definition of its species and their
behaviour in aqueous solution a difficult and frustrating experimental problem. Conflic-
ting reports in the literature abound simply because most conclusions from experiment
must be speculative. We shall describe, in the space allotted, the nature of aqueous species
for each oxidation state over the pH spectrum, and typical complexes so far characterised.
We shall also describe such redox chemistry as can be defined, and catalytic behaviour of
MO as a trace element.

MOLYBDENUM(W)
(a) Moo4 2 - and isopolyacids
Molybdenum(V1) is generally found at pH > 6 as tetrahedral [ 1] , colourless Mood2 -
which may be compared to yellow Cr04 2 - in which L-M transfer bands of low energy
overlap the visible-u.v. border. Both undergo acid hydrolysis and polymerisation with
very different results. Whereas Cr(VJ) remains tetrahedral with corner sharing in Cr20T2-
and (CrO&, Mo(VI) becomes octahedral while forming polyacids and anions [2] _Acid
hydrolysis of Mood2 - gives M0702 46- and MosO264 - from pH 1 to 6. Monomeric

*Presented at the Conference on “The Chemistry and Uses of Molybdenum”, at the University of
Reading, England, September 17 - 21, 1973, sponsored by Climax Molybdenum Co. Ltd., and the
Chemical Society (Dalton Division).
96

complexes of cis-Moos’+ appear in strong acid [2]. Log Kf values for the formation of
various oxomolybdate(V1) species from nM004~- and mH’ are HMo04- (3.5), H2M004
or HeMoO (7.3) M0,024 6 - (52.4), HMo,024’ - (57.2), Mog0244 - (72.25).
Reactions of Moo42 - which expand its coordination number from four to six are
extremely fast. MO~024~- is formed sufficiently rapidly in a flow mixing device to inter-
fere with measurement of protonation constants for Moo42 - [3] . This is in contrast to
the relatively slow formation of Cra0,2:

(b) Complexes of Mo022+

Strongly acid solutions depolymerise MO, and Mos polyacids yielding complexes of
~is-MoO~~+,which has a characteristic Raman spectrum [4]. MoO~C~~(H~O)~and Moo2
C142- have been observed in hydrochloric acid solution [2] .
MOODY-reacts with poly-01 and polyamine chelating agents. At pH 5 - 7 catechol
forms a 2: 1 complex [5] .
2C,H4(OH), t Moo42 -+ (CJI4O2)2 Mo02’- t 2HaO.
At pH = 0 - 1, a 1: 1 complex is formed. Apparently high acidity inhibits coordination to
catechol as it does polymolybdic acid formation.

(c) Complexes of Moo3

Polydentate ligands may form octahedral complexes with MoOa. Diethylenetriamine
(dien) forms water-soluble dienMoOs [6]. Hexadentate mannitol [7] and EDTA [8] form
1:2 complexes with Mo(VI), which may have two Moos bridged by one ligand and each
using three ligand donor sites. Oxalate forms a dinuclear complex with [OQMOOMOO~] 2+
with one Ca042- and one Hz0 joined to each Mo(V1) [9].

(d) Hereropolymolybdares
When solutions of Moo42 - are acidified in the presence of many tetrahedral oxy-
anions or positive metal ions M0raO4e*- forms, containing a central tetrahedral hole in
which Si4+,As’+, Co3+,etc. may fit [lo]. Octahedral holes are formed by M0eO24~~-
which can accomodate six coordinate ions in the centre, such as Mo6+in the isopolyacids,
and Te6+. Pope [l I] has distinguished two types of polyacid: (I) has one terminal oxygen
on each peripheral MO,as in XMorsO4e’; and (II) has two cis terminal oxygen atoms on
each MO,as in mo6024n: Type (I) acids behave analogously to tetragonal monomeric
species O=Mo, whereas type (II) acids behave analogously to cis-Mo022+ monomeric com-
plexes.

(e) Substitution reactions of Mo( VI) species.

Bubbling H2S through aqueous M004~ - produces Mo03S2 -, M00a$~ -, MoOSs2 -
and MOSER- [12] . In general, oxo-ions where oxygens are bridging or terminal, appear to
be easily interconvertible with thiomolybdates(V1) or (V). As may be noted, substitution
by Cl- requires assistance from H’ and expansion to six coordination. 022- substitutes for
O2 - in polyacids [3] .
 97

MOLYBDENUM(V)

MoOCls * - is the best characterised MO(V) species in aqueous systems. The green,
monomeric, paramagnetic ion [4] exists in HCl solutions of concentrations > 10 M. It
has been shown spectrophotometrically that as water is added, dimerisation takes place,
with maximum enhancement of the dimer spectrum at - 5 M HCl [ 151.
There is a general reduction in paramagnetism as the HCl concentration is decreased
further until, at - 2.5 M, the MO(V) species is diamagnetic [ 161. The disappearance of
monomeric species is more rapid than the overall decrease in paramagnetism, indicating
that the dimer formed may be paramagnetic [ 171.
There is spectrophotometric evidence for two dimerisation steps, each involving
loss of two protons [15] and the formation of a tetramer from the second dimer [ 181.
The following oxomolybdenum(V) moieties, bound to other ligands with MO in octa-
hedral sites, have been isolated from aqueous acid.

KO Hz0 40
2Mo03+ T+, Mo2036+ 2 Mo2042+ Z %Mo401,,.
t t t
2H’ 2H’ 2H’

The principle evidence for these moieties is the isolability of solids which contain them.
No definitive studies of either structure or equilibria in solution are available.
In contrast to the behaviour of [MoOCls] *-, it has been found that the oxopenta-
bromide ion, [MoOBrs] * ; is not the principal species in concentrated (8.6 M) HBr [ 19,
201. Rather, the predominant species is the ion [MoOBr4]; which may be isolated from
solution in either hydrated or unhydrated form. The ion is dimeric in solution and
bridging through bromide has been suggested [20 1. A spectrophotometric investigation
of hydrolysis products in HBr has indicated the existence of three other dimeric species,
including the ion [Mo202(OH)2Br4] .8H20 at 6.5 M HBr [20]. At higher MO(V) con-
centrations [20] studies indicate the formation of tetrameric species which are para-
magnetic at higher acid concentrations and diamagnetic at lower acid concentrations.
A formulation involving the central moiety [Mo40r0] ’ was suggested for the diamag-
netic species [2 1] .
The monomeric complex, M2’ [MoO(NCS)s] , and the dimeric ions M,I [M0203
(NCS)a] and M,’ [Mo204NCS)e], may be prepared from M21[MoOCIs] in aqueous
thiocyanate solutions [22].
No monomeric species other than the ones mentioned above have been isolated
from aqueous solution. This is undoubtedly an effect of the very great tendency of
MO(V) to dimerise. Monoxo- and dioxo-bridged dimeric MO(V) complexes have been
prepared from aqueous solution, the complexes being either anionic or electrically
neutral.
A review of monoxo- and dioxo-bridged dimeric MO(V) complexes which may be
prepared from aqueous medium has been compiled elsewhere [ 14 1. The following
discussion will be confined to isolab le complexes which are soluble and stable in water
solution.
Very few MO(V) dimeric complexes meet the above criteria, since most of the
98

known complexes of M0s0~~’ and Mo20a4+ are uncharged and sparingly soluble in
water. All monoxo-bridged dimers known to us with chelating ligands are uncharged.
Well-characterised, anionic, dioxo-bridged dimers, which have been the subject of aqueous
solution studies, include Na2 [Mo204(EDTA)] *Hz0 (structural study by p.m.r.; redox
behaviour) [23,24], Na2 [Mo204(oxalate)2(H20)2] (ligand substitution reactions [25],
and Na2 [Mo204(cysteine),] *2H20 (base hydrolysis reactions, and as a chemical model
for molybdenum-containing enzymes) [26 - 291.
In the oxalate complex it is noteworthy that monodentate ligands exchanged with
water, but that bidentate ligands promoted cleavage of one of the oxo-bridges, producing
uncharged monoxo-bridged species [Mo20s(oxalate),(bident)z] ’ [25] .
As was previously mentioned, the implication of MO(V)in enzymatic redox reac-
tions has produced a great deal of interest in MO(V) dimers, particularly in those which
contain a bound thiol group. This topic was reviewed in 1969 [30], and since that time
the work of several investigators has focused either directly or indirectly on the third of
our examples, [Mo204(cysteine)2] 2: Schrauzer [29] has shown, for example, that a basic
aqueous solution containing MO(V), cysteine, ATP, and a reducing agent, can emulate
many of the chemical reactions of the enzyme nitrogenase. The work of other investiga-
tors has shown that the cysteine complex reacts with aqeuous base to break the oxo-
bridges, forming both monoxo-bridged [27] and monomeric species [28]. The mono-
meric species is e.s.r. active, yielding a 6-line spectrum when the complex is isotopically
enriched with “MO.
In related work, a paramagnetic dimer coordinated to glutathione was detected in
basic aqueous solution by e.s.r. [31]. Glutathione serves as a bridge between the molyb-
denum centres, keeping them in proximity to one another even though the oxo-bridges
are broken. This behaviour is evidenced by an 1 l-line e.s.r. spectrum, due to equivalent
interacting molybdenum centres, produced by a sample enriched in “MO.
The significance of this result in terms of an enzyme model is that the molybdenum
centres are held relatively close to one another, as they may be _man enzyme matrix,
while, at the same time, binding sites are made available and the paramagnetism which is
generated in the active enzymes is emulated.
Several bidentate ligands have formed paramagnetic dimers with Mo20a2+ in aqueous
solution. M0204Ls complexes are formed with the ligands HS-CHs-CHs-NH?, and
HS-CH2-CH2-COOH 1321. One bidentate ligand would necessarily form a bridge bet-
ween the metal centres. Such complexes exhibit behaviour in basic solution similar to
that of the glutathione complex, “MO-enriched samples of each complex exhibiting the
1l-line e.s.r. spectrum expected for paramagnetic dimers. Mo~O~I_Q~-forms with
HSCH2CH2SH giving a 6-line e.s.r. spectrum with “MO like cysteine. However, similar
solutions containing ligands which do not have a thiol group did not develop an e.s.r.
signal at all under similar conditions. Thus, e.s.r. spectra may be useful in defining MO(V)
environments in enzyme complexes.
Finally, the authors and others have isolated, from acidic aqueous solutions,
tetrameric MO(V) complexes of the general composition [Mo40re(lig)], with’glutathione
[33] and related large hexadentate ligands derived from cysteine [34]. Previous evidence
for tetrameric MO(V) complexes in aqueous solution was produced by the hydrolysis of
M,’ [MoOXs].Complexes of the composition [Mo40sXs(Hs0)2] 4 - have been isolated in
non-aqueous solvents [ 181.
 99

MOLYBDENUM(W)

The only well-known Mo(IV) species in aqueous solution is [Mo(CN)s] 4; a substi-

tution inert diamagnetic species. The structure of the ion in aqueous solution is in dispute
as between square antiprismatic and dodecahedral [35]. The ion, despite its high charge,
is remarkably indifferent to association with positive species. No evidence of protonation
is seen up to 3 M HC104 [36]. Divalent ions precipitate hydrated Mz [Mo(CN)a] salts
which show no effects of M-N association beyond a slight broadening of the CN stretch-
ing band in the i.r. spectrum. Weak association with trivalent ions, Fe3+ [36] and Cr3+
[37], has been observed, FeMo(CN)a- having a Prussian blue-like appearance and a Kf of
only 90 in 1 M HC104.

Oxidation of [Mo(CN)s] 4-
The reaction

[Mo(CN)s] 4 - $ [Mo(CN)s] 3 - t e- (E, = 0.8 V)

is reversible. Outer sphere electron exchange between Mo(IV) and MO(V) cyanides is very
fast [38] . HCr04- oxidises [Mo(CN)a] 4 - by way of electron transfer through CN-
bridged intermediates [39] .
0x0- or aquo-Mo(IV) species are only indirectly observed since Mo(IV) products of
reduction of Mo(V1) undergo rapid disproportionation [40] analogous to Cr(IV) [41].
(See catalytic processes.) The rate constant of the disproportionation reaction, kz, has
been estimated as - lo4 at 298 K [40].

MOLYBDENUMCIII)

The chemistry of molybdenum(II1) complexes in aqueous solution has not been

extensively investigated.
Salts of [Mo(III)Cl,] 3 - are soluble in water, and stable in aqueous HCI > 9 M. At
lower concentrations [MO&] 3- forms [MoC1s(H1O)] * - (1 - 2 M) and undergoes sub-
stitution reactions with various bidentate ligands (oxalate, EDTA, in, o-phen, bipy) [42].
The hexaisothiocyanate ion [Mo(NCS),] 3+ is known, and is stable in water [43].
Also, two cyanide complexes, K2 [Mo(CN)s] [44] and K4 [Mo(CN),(H,O)~] [44,46]
are known, and are stable in aqueous solution.
Depending on conditions of acidity, the yellow ion [Mo(H20),] 3+, and its dimeric
counterpart can both be isolated from aqueous solution in the absence of other co-
ordinating moieties [47], The green, dimeric Mo(II1) species frequently encountered in
aqueous solution is probably the dioxo-bridged species [MozO,] *+, as is evidenced by
the preparation of [Mo202(EDTA) (2H,O)*] *- (green) by electrolytic reduction of
[Mo(V)~O,(EDTA)] * - [48].

MOLYBDENUMW)

The metal cluster ion [Mo6C1a] 4+ is stable in aqueous acid [49] . Each MO atom in
the face of a cube is a binding site for the formation of [MoClsLe] “.
100

[(MoeCla)Cle] 2- is stable in concentrated HCl solution. As the acidity of the

solution is lowered, (OH)- is substituted for Cl- [50] to make the complex [(Mo6Cls)-
(OH),] 2 : The rates of chloride exchange and bromide substitution have been studied in
aqueous solution for the chloro complex [5 1 ] , as have the rates and mechanism of
alkaline hydrolysis for substitution into the [Mo,Cls] 4+ moiety [52]. [(Mo,Brs)(Br),] is
polymeric, whereas [(MoeBrs)(Br)e] 2 - is monomeric [53]. Complexes of &-bonded
MOBS+including octahalides and the hydrate have been studied in aqueous solution [47].

OXIDATION-REDUCIION AND CATALYSES BY MO(W), (V), (IV)

Stiefel [54] has recently suggested that the ability of molybdenum complexes to
furnish sites for concerted electron and proton transfer may be the key to its enzymatic
function. Many complex molybdenum species undergo redox processes coupled to proton
transfer without significant structure change; for example:

(VI) + blue
SiMoi204e4- + ne- t nH’ 2 H,SiMoi204e4-

where n may be as high as 8 overall [56]. Reductions occur in one or two-electron steps.
E”‘s vary from fl.2 to -0.5 for various steps.

(VI) + (IV)
[MoOsCl4] 2- + 4H’ f 2e- + [Mo(OHs)sC14]
Ea =0.15 v [57]

09 + (III)
[MoOCls] 2- t 2e- t 2H+ f [Mo(OH),Cls] ‘-
_!?’ = -0.38 V [56]

[Mo204EDTA)] 2 - t 4e- t 4H’ * [Mo~O~(EDTA)(H~O)~] ’ - [8].

Mo7024 6 - is decomposed on reduction. Irreversible polarographic reduction of

Mo(V1) + MO(V) -+ Mo(II1) in two steps is common in acid media.
In buffers, pH 3-8, MO(V) monomers are rapidly oxidised [30] , but in 6 - 10 M
HCl, MoOC1s2- neither reduces nor catalyses reduction of C104: [MoC16] 3- is inert to
oxidation by ClO,-; MOTORS+is labile; and Mo(H~O)~~+ is very fast.
Coordination of various oxo-ions and molecules such as NOs; C104; NHsOH,
H202, and perhaps N2, to Mo(VI), MO(V) and MO(W), lowers their activation energy for
reduction. This chemistry is of great importance to the understanding of molybdenum
function in enzyme catalysed reductions of nitrate, nitrite, nitrogen and oxidation of
xanthine and sulphur dioxide.
In simple aqueous systems, complicated rate laws usually show half-order depen-
dence on molybdenum, e.g., Sn(I1) and C104- [58],

Rate = ki [Sn(II)]3’2’ [C104-]3/2 [MO]‘/’ /(l + K[C104-I).

In catalytic reductions of C104- and N03- in > 1 M HCl, all oxidation states except (IV)
may be ruled out, on chemical evidence, as the catalytic species [58] . Catalytic polaro-
graphic waves due to C104- reduction occur in conjuction with waves assigned to
MO(W) + (IV) and MO(V) + (III) reductions. Mo(IV) is very unstable, disproportionating
 101

rapidly, leading to the observed half-order dependencies. Disproportionation is competi-

tive with diffusion out of the reaction layer of a dropping mercury electrode at 10m4 M
MO(W). Reactions of MOTORS+also may show half-order dependence, but in at least two
cases clear distinctions between MO(V) reduction and MO(W) catalysis have been made
[59,60]. One important function of the protein of a molybdenum-containing enzyme
may be to hold atoms apart to prevent disproportionation of (IV) and dimerisation of
(V) from inhibiting the catalytic function.

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