Research: Science and Education

edited by
Products of Chemistry George B. Kauffman
California State University
Fresno, CA 93740

Polypyrazolylborates: Scorpionates
Swiatoslaw Trofimenko
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716; trofimen@udel.edu

In introductory chemistry courses the concept of the

chemical bond is of major importance. Various types of
chemical bonds such as ionic, covalent, and coordinate co- 4 R ″
valent are presented and explained, and shown in what sys-
5 3 R⵮
tems and compounds they are found. It is pointed out that R ′
numerous chemical compounds are actually coordination Hn B N N
Rn B N N
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1 2
complexes. Many of them, based on rather complicated 4 −n 4 −n
ligands, are important in major life processes. For instance
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chlorophyll, the ultimate basis of all life on the planet, is a

coordination compound of magnesium; vitamin B12 is a co-
ordination compound of cobalt; hemoglobin in our blood is
a coordination compound of iron; hemocyanin of inverte-
brate blood is a coordination compound of copper; and there
are many other examples.
Coordination compounds and complexing agents are
used in everyday life as, for instance, in extraction, dyeing,
leather tanning, electroplating, catalysis, water softening, and
other applications. Although in introductory chemistry
courses simple ligands such as water, ammonia, chloride, and
other inorganic ions are discussed, there are more complex
and unusual ligands that can motivate, interest, and excite
beginning students.
In organometallic and coordination chemistry the choice
of a ligand is important, whether to effect catalytic activity
for some chemical reaction, to model a bioinorganic enzyme
system, or to achieve other goals. Among the most often used
uninegative ligands the two outstanding examples are the cy-
clopentadienyl and the beta-diketonate anions, including
their variants, such as substituted cyclopentadienyl ligands,
or beta-diketonates where the oxygen atoms have been re-
placed by sulfur or by arylimido moieties.
Polypyrazolylborate Anions
In 1966 a versatile new class of ligands appeared, com-
bining some features of the cyclopentadienide and beta-
diketonate ligands (1). About two thousand articles have been
published on the chemistry of these new ligands, complexes
of these ligands with 70 elements of the periodic table have
been reported, a book covering the literature up to late 1990s
(2) and numerous reviews (3–22) have been published cov-
ering this subject, and a special symposium was devoted to
these ligands at the April 2003 ACS Meeting (23). Clearly
these ligands should be an integral part of inorganic courses,
both lecture and laboratory. And yet, this ligand class has re-
ceived only scant attention in textbooks of inorganic chem-
istry. These new ligands are the polypyrazolylborate anions,
of general structure [RnB(pz)4-n]−, where n can be 0, 1, or 2,
pz is a pyrazol-1-yl group, and R can be H, an alkyl, or aryl
group (Figure 1).
Figure 1. General structure of polypyrazolylborate anions,
[RnB(pz)4-n]−, where n can be 0, 1, or 2, pz is a pyrazol-1-yl group,
and R can be H, an alkyl, or aryl group.
Synthesis
These ligands can be synthesized by many different
routes (2), but most easily by the neat reaction of pyrazole
(or substituted pyrazole) with a borohydride anion in the
absence of solvent. The reaction of unsubstituted pyrazole is
shown as follows:
−
[H2B(pz)2]
or
− −
[BH4] + excess Hpz [HB(pz)3] + nH2 (1)
or
−
[B(pz)4]
Temperature control steers this reaction to produce selectively
only one of the above products. With asymmetric pyrazoles,
such as 3-R-pyrazoles, this reaction proceeds with boron be-
ing bonded to the least hindered nitrogen atom. The only
exceptions are indazole (benzopyrazole) and indazoles with
substituents at positions other than 7, which bond through
the more hindered nitrogen atom (24, 25).
Naming
When n is 1, and R is H, we have the parent tridentate
ligand [HB(pz)3]−, which is analogous to the Cp ligand in
being uninegative, providing six electrons, and occupying
three coordination sites in its complexes. It has been given
the abbreviation Tp, and its substituents are denoted by su-
perscripts. The “default” position in this abbreviation system
is the 3-position on the pyrazole ring (Figure 1), which is
denoted by a superscript “R”, that is, TpR. Thus, the 3-phe-
nyl analogue of Tp is written as TpPh (11).

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 Research: Science and Education

Bonding scorpionates), or other (H, OR, SR, NR2) group (hetero-

Since the systematic name poly(pyrazol-1-yl)borates is
cumbersome and does not convey the mode of coordination
of these ligands, the moniker “scorpionates” was coined (11),
which provides an idea of how the ligand bonds. Almost al-
ways two pyrazolyl groups (claws) are coordinated to the
metal ion (Figure 2), and the resulting six-membered ring is
in a deep boat form that brings the third pyrazolyl (homo-
R⬘
R B
N N
N N
scorpionates), like the tail of a scorpion, arching over and
“stinging” the metal ion. The point here is that the “sting” is
not mandatory, since the Tp ligand can sometimes be only
bidentate (κ2), as in complexes of Rh(I) and Pd(II).
Most of the work with scorpionates was done with the
parent Tp ligand and with Tp* [= HB(3,5-Me2pz)3], both
analogues of Cp. Compared to Cp, the Tpx ligand offers more
choices of modifying its steric and electronic features by sub-
stitution on the pyrazolyl rings and on boron, having ten sub-
stitutable positions compared to just five for Cp. Moreover,
while only R5Cp ligands retain the original symmetry of the
Cp ligand, in the case of Tp many substitution types are pos-
sible with retention of the original C3v symmetry as, for in-
M stance, TpR, Tp4R, TpR2, TpR3, RTp,1 and many others. Even
minor changes in substitution, such as replacement of a 3-H
and 5-H by 3-Me and 5-Me, as in Tp* = TpMe2, can affect
the chemistry; for instance,

{Mo[HB(pz)3](CO)3]}− + [ArN2]+
Figure 2. Bonding in a polypyrazolylborate–metal complex.
(2)
TpMo(CO)2(N NAr)

{Mo[HB(3,5-Me2pz)3](CO)3]}− + [ArN2]+
(3)
Tp*Mo(CO)2(η2-COAr)

Also note that the progressive increase in steric hindrance of

N N N N
N N
N N Tp ligands can affect the depth of the hydrophobic pocket
around the metal as shown in Figure 3.
H B N N M H B N N M H B N N M H B N N M
While the Tp and Tp* ligands readily yield octahedral
N
N N N N N N N complexes M[Tp]2 and M[Tp*]2 with first-row transition
metals, the presence of a 3-t-butyl group in TptBu prevents
formation of octahedral complexes and leads predominantly
to tetrahedral species M[TptBu]X. The TptBu ligands have
accounted for a number of striking new developments in co-
Figure 3. Increasing hydrophobic environment around the metal
ordination chemistry, such as stabilizing monomeric alkyl-
ion owing to steric hindrance of the substituted polypyrazolylborate magnesium (26–28), alkylzinc (29, 30), and alkylberyllium
anion. Note that ⫺N – N⫺ is the third pyrazolyl ring. species (31); novel oxygen complexes (32); and zinc-based
enzyme models (33, 34). The Tl(I) salts of Tpx complexes
are useful for the isolation and purification of the ligands,
and they are soluble in organic solvents. Tl[Tpx] species are
almost always monomeric in the crystal. A striking excep-
tion is the tetrameric {Tl[Tpcpr]}4, where cpr is cyclopropyl,
the structure of which consists of a perfect tetrahedron of
Tl atoms, each apex being capped by a Tpcpr ligand (Figure
4).
The ease of synthesis of scorpionate ligands and of their
complexes can be readily utilized in teaching inorganic syn-
thesis. For instance, the synthesis of KTp* can be carried out
in one laboratory session (35). Its conversion to the yellow
[Tp*Mo(CO)3]− anion, followed by in situ treatment with
butyl nitrite, yields the neutral orange complex
TpMo(CO)2NO (36, 37).

Hpz*(excess) + KBH4
(4)
K[HB(pz*)3] (= KTp*) + 3H2

Figure 4. The structure of {Tl[Tpcpr]}4. Three of the apical Tpcpr ligands

have been omitted, for the sake of clarity. KTp* + Mo(CO)6 K[Tp*Mo(CO)3] + 3CO (5)

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 Research: Science and Education

K[Tp*Mo(CO)3] + BuONO
(6)
TpMo(CO)2NO + CO + KOBu

The denticity of a Tp ligand can be extended beyond κ3

by including 3-substituents with additional donor atoms. For
instance, TpPy, which contains a 3-(2-pyridyl) substituent, is
κ6 in its icosahedral complexes of U(III) and Sm(III) (38).
An example of a hexadentate N3O3 ligand is Tp with a 3-
carboxypyrrolidido substituent, TpCONC4H8. While in crystals
of its lanthanide complexes [TpCONC4H8]2(anion) one ligand
is κ6 and the other κ4, with one arm detached, in solution
there is a rapid exchange of the coordinated and free pyrazolyl
arms so that all arms are magnetically equivalent (39). By con-
trast when the 3-substituent is carboxy-t-butylamido, the
TpCONHtBu ligand is κ6 in the crystal as well as in solution of
its in lanthanide complexes (Figure 5) (40).

Applications of Borate Scorpionates Figure 5. Structure of the cation {La[TpCONHtBu]2}+.

Some examples in which polypyrazolylborate ligands have

been employed in the synthesis of complexes that had, inter
alia, catalytic activity in various reactions, or served as models
of biologically active complexes, are discussed briefly below.
Enzyme Modeling
Complexes of diverse scorpionate ligands were used to
mimic the activity of enzymes containing various metals, usu-
ally providing an environment similar to that of three coor-
dinated histidine nitrogens. For instance vanadium complexes
of general type Tp*VO(OAr)2 have been considered as pos-
sible models for the active site in bromoperoxidase (41). In
the case of molybdenum, various Tp complexes were em-
ployed to model the mononuclear molybdenum cofactors of
molybdopterin enzymes, such as xanthine oxidase–dehydro-
genase, sulfite oxidase, nitrate reductase, and dimethyl sul-
foxide reductase (42–48). Similar complexes were also
employed in mimicking sulfur-containing tungsten enzymes,
such as aldehyde oxidoreductase, formate dehydrogenase, and
formylmethanofuran dehydrogenase (49–51). Mimicking the
activity of manganese superoxide dismutase and of various
binuclear manganese enzymes active in redox functions, was
approached with TpiPr2Mn(OBz) and related binuclear com-
plexes (52–54).
In the area of iron-containing enzymes, the behavior
of the oxo-bridged diiron enzyme hemerythrin was approxi-
mated with complexes such as [TpFe]2(µ-O)(µ-OOCR) and
[TpFe] 2(µ-OH)(µ-OOCR) (55–58), while the complex
TpiPr2Fe(OOCPh)(µ-O)(µ-OAc) was regarded as a synthetic
model for the dioxygen binding site of nonheme iron pro-
teins (59). Other related complexes were regarded as struc-
tural and functional models of catechol dehydrogenases (60)
and of methanol monooxygenase (61). Complexes such as
Tp*Ni(OEt-cysteinato) were studied as being of relevance to
the nickel component of the active site in several hydroge-
nase enzymes, which participate in the bio-generation of hy-
drogen and methane, as well as in nitrogen fixation (62).
Copper is present in a variety of enzymes, and the use of
scorpionate–copper derivatives for modeling purposes has
been reviewed (63). Specific complexes were used for model-
ing the active site in phenylalanine hydroxylase (64), the cop-
per–ethylene binding sites in plants (65), the copper center
of galactose oxidase (66), in poplar plastocyanin (67), in blue
copper proteins (68–71), in mixed-valence dicopper electron
transfer sites of the enzymes nitrous oxide reductase or cyto-
chrome c oxidase (72), and in oxyhaemocyanin and
oxytyrosinase (73–75).
Much work has also been done in zinc complexes related
to carbonic anhydrase, and the complex TptBu,MeZn(OH)
proved to be a good functional model for that enzyme (76,
77). The catalytic cycle of liver alcohol dehydrogenase was
modeled by [TptBu,MeZn]L species (78), while other complexes
mimicked the activity of alkaline phosphatase (79). The ac-
tivity of cobalamine independent methionine synthase was
approached through complexes such as Tp*ZnSR and
TpPh,MeZnSR (80).
Catalysis
Certain Tpx complexes were found to catalyze a variety
of chemical reactions, including polymerization and oligo-
merization. For example, the complex Tp*W(⫽NPh)
Br(⫽CHPh) and related complexes when combined with
AlCl3 catalyzed the acyclic diene methathesis (ADMET) of
1,9-decadiene and also the ring-opening metathesis (ROMP)
polymerization of cyclooctene (81–83). Similar activity was
found in analogous molybdenum complexes (84). Terminal
alkynes were dimerized by neutral Ru(II) complexes such as,
for instance, TpRuCl(PPh3)2 (85), while TpRu(⫽C⫽CHPh)
(Cl)(PPh3) achieved ROMP polymerization of norbornene
(86). Phenylacetylene was homopolymerized by species such
as TpR2Rh(COD) (87). The sterically hindered complex
TptBuMg(OEt) was a precursor for rapid stereoselective ring-
opening polymerization of L,L-dilactide to yield isotactic
poly(L,L-lactide) (88).
Ethylene was polymerized by activated
TpxNbMe2(PhC⬅CMe) (89), by Tp*V(⫽NAr)Cl2 (90), and
by Tpx yttrium complexes that required no cocatalysts (91).
Stereoregular copolymerization of ethylene and carbon mon-
oxide was catalyzed by TpPhNi(PPh3)(o-Tol) (92).

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 Research: Science and Education
C–H Bond Activation
Activation of aliphatic and aromatic C⫺H bonds was
by photolysis of the Tp*Rh(CO)2 complex, which proceeded
with loss of CO and oxidative addition of ArH or RH (93–
96). Many other examples of C⫺H activation are listed in
section 5.4 of ref 1. More recent examples employed TpxCu
species to effect cyclohexane and benzene amination (97) and
insertion of the CH2COOEt moiety into C⫺H bonds of hy-
drocarbons and ethers (98).
Carbene and Nitrene Transfer
The complex Tp*Cu(ethylene) catalyzed the reaction of
ethyl diazoacetate with olefins to form cyclopropanes and also
catalyzed nitrene transfer from PhI⫽NTs to form aziridines
(99–101). The cation [Tp*W(⫽CH2)(CO)(PhCCMe)]+ was
also active in similar reactions (102). More recent work
showed that the efficiency of carbene transfer by TpxCu com-
plexes was related to the substituents on the Tp ligand (103,
104). Thus, the ligand TpMs (Ms is mesityl) was outstanding
for the cyclopropanation of olefins (105), but in the carbene
transfer to acetylenes TpCy (Cy is cyclohexyl) was the stellar
performer (106).
Other Scorpionate Ligands
Although polypyrazolylborates are archetypal examples
of the scorpionate ligand system, related scorpionate ligands
may be obtained by replacement of either the central boron
or the pyrazole. A number of such examples have been cov-
ered earlier (35). Neutral analogues are best exemplified by
geminal polypyrazolylalkanes that were introduced in 1970
(107).
There are also non-pyrazolyl scorpionate ligands, con-
taining a boron core. They are of the type [Ph2B(CH2Z)2]−
and [PhB(CH2Z)3]−, where Z can be a variety of donor func-
tionalities. Examples of Z = SR for both types (108, 109) of
Z = PPh2 for [Ph2B(CH2Z)2 (110, 111), for [PhB(CH2Z)3]−
(112, 113), and for Z = NMe2 (114), have been reported, as
have those containing, in addition, a pyrazolyl substituent
(115).
The chelate ring size is another adjustable variable, lead-
ing to ligands such as [RB(CH2Z)2(ER)]−, where E = O, S,
Se, or appropriate phosphino or amino functionalities. Re-
lated polypyrazolylborate examples, containing two pyrazolyl
bridges and one dimethylamino (116), or arylmercapto
(117), or alkoxy bridge (118), have been reported earlier.
While chelates derived from the above ligands involve
five- and six-membered rings between boron and the coor-
dinated metal, other ligands lead to eight-membered rings.
These ligands are represented by hydrotris-(mercapto-
imidazolyl)borate (119, 120) and the related hydrotris(thi-
oxotriazolyl)borate (121). The former contains twisted
eight-membered rings in its complexes that are always sulfur
bonded, while the latter is ambidentate and bonds either
through sulfur (with bismuth or tin) or through nitrogen
(sodium or manganese). Dihydrobis(thioxo-triazolinyl)
borate, a still different ligand, bonds in tridentate fashion
through two sulfurs plus an agostic hydrogen bond (122,
123).
1718 Journal of Chemical Education • Vol. 82 No. 11 November 2005
Conclusion
As we can see from the foregoing, scorpionate-type
ligands and particularly the original polypyrazolylborates are
easy to synthesize, have good stability, and are, in general,
quite user-friendly. They also have well-defined spectroscopic
tags in their NMR and IR spectra (sharp B⫺H stretch).
Their thallium(I) salts are readily soluble in organic solvents,
which permits their use in organic media, or in two-phase
aquo–organic solvent mixtures. All these features should
make them useful in the teaching of coordination chemistry,
both in lectures and in the laboratory, providing relatively
easy yet instructive examples of synthesizing coordination
and organometallic complexes.
Note
1. The superscripted R indicates substitution at the 3 posi-
tion on the pyrazol group; superscripted #R indicates substitution
at a position other than the third position; superscripted R# indi-
cates multiple substitutions; and RTp indicates substitution of the
H bonded directly to the boron atom.
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