435

10
Metal Borides: Versatile Structures and Properties
Barbara Albert and Kathrin Hofmann

Technische Universität Darmstadt, Eduard-Zintl-Institute of Inorganic and Physical Chemistry,

Alarich-Weiss-Str. 12, 64287 Darmstadt, Germany

10.1
Introduction

Boron is a non-metallic, light element with three valence electrons. Its ability to
form multi-centered bonds to overcome the electron deficiency is huge, and it
manifests itself in an enormous variety of complicated structures, often charac-
terized by boron atom polyhedra. Boron allotropes, such as α- and β-rhombohe-
dral boron (these are the two modifications most stable under ambient
conditions), contain icosahedra of boron atoms (Figure 10.1) that are three-
dimensionally interconnected (Figure 10.2).
Many metals react with boron and form borides. Metal borides (MxBz,
MxM´ yBz, etc.; M, M´ = metals) are binary or multinary compounds in which
boron is the most electronegative partner. Thousands of borides are known,
their compositions ranging from M∼7B to MB∼80: M5B, M3B, M5B2, M7B3, M2B,
M5B3, M3B2, M11B8, MB, M10B11, M3B4, M2B3, M3B5, MB2, M2B5, MB3, MB4,
MB6, MB10, MB12, MB15, MB18, MB66.
Borides represent an important class of inorganic solids. Often they exhibit
interesting properties and can be used either as structural and functional materi-
als or as catalysts. Table 10.1 gives a glimpse on binaries of the main group ele-
ments that were confirmed to exist [1]; many more have been described. Even
more borides are formed by transition metals (Table 10.2) and rare earth ele-
ments (lanthanoides in Table 10.3) [2,3]. Among the borides of the actinoides, it
is ThB4, ThB6, and UB12 that have been investigated most. These three com-
pounds will be discussed in Chapter 10.4, but otherwise borides of radioactive
elements are omitted in this book. Several of the formulae in Tables 10.1 and
10.2 are marked by an asterisk, indicating that they crystallize with structures
similar to that of the so-called β-rhombohedral boron (Figure 10.2), where metal
atoms are located on interstitial positions, and both boron and metal atom posi-
tions may be partially occupied only. This leads to some uncertainty in terms of

Handbook of Solid State Chemistry, First Edition. Edited by Richard Dronskowski, Shinichi Kikkawa, and
Andreas Stein.
 2017 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2017 by Wiley-VCH Verlag GmbH & Co. KGaA.
436 10 Metal Borides: Versatile Structures and Properties

Figure 10.1 Boron atom icosahedron, the most important structural entity in elemental boron
and boron-rich metal borides (boron atoms: red).

Figure 10.2 Crystal structure of β-rhombohedral boron, one of the allotropes of the element.
(Figure from Ref. [1].)

Table 10.1 Binary borides of main group metals.

LiB1 x BeB3
Li2B6 Be3B50
Li3B14
LiB10∗
Na3B20 MgB2 AlB2
Na2B29 MgB7 AlB12
NaB28∗ Mg5B44 AlB31∗
MgB12
MgB17.9∗
KB6 CaB6
SrB6
BaB6
∗
indicates a β-rhombohedral boron-type structure.
 10.1 Introduction 437

Table 10.2 Binary borides of d-group elements.

ScB2 TiB V3B2 Cr2B Mn2B Fe23B6 Co23B6 Ni23B6 CuB28∗ ZnB25∗
ScB12 Ti3B4 VB Cr5B3 MnB Fe3B Co3B Ni3B
ScB15 TiB2 V5B6 CrB Mn3B4 Fe2B Co2B Ni2B
ScB78∗ V3B4 Cr3B4 MnB2 FeB CoB NiB
V2B3 Cr2B3 MnB4 FeB4 Co5B16 Ni4B3
VB2 CrB2 MnB23∗ FeB49∗ Ni7B3
CrB4 NiB48.5∗
YB2 YB4 ZrB Nb3B2 Mo2B Ru7B3 Rh7B3 Pd6B — —
YB6 ZrB2 NbB Mo3B2 Ru11B8 Rh5B4 Pd5B
YB12 ZrB12 Nb5B6 MoB RuB RhB Pd3B
YB66 Nb3B4 Mo2B4 Ru2B3 Pd5B2
Nb2B3 MoB2 RuB2 Pd2B
NbB2 Mo1 xB3
LaB4 HfB Ta2B W2B Re3B OsB IrB0.9 Pt4B — —
LaB6 HfB2 Ta3B2 WB Re7B3 Os2B3 IrB Pt2B
TaB WB2 ReB2 OsB2 IrB1.1 PtB
Ta5B6 W2B4 IrB1.35 PtB0.7
Ta3B4 W1-xB3
TaB2 WB4
∗
indicates a β-rhombohedral boron-type structure.

an accurate M:B ratio, and the compositions of these compounds were approxi-
mated only.
While almost all of the metals of the periodic system do form borides, no
binaries are known for the systems Rb–B, Cs–B, Hg–B, Ag–B, Au–B, Ga–B, In–
B, Tl–B, Sn–B, Pb–B, and Bi–B. Furthermore, these combinations do not show
any (or almost no) solid solubility in each other.
Surely, it is the combination of certain physical properties that make metal
borides in general interesting [3]. Common to many borides is their highly
refractory character, and others have been described repeatedly: (super)hardness,
(ultra)incompressibility, and thermal stability [4]. These properties lead to exist-
ing or potential applicability for the hardening of tools or thermal or

Table 10.3 Binary borides of the lanthanides.

CeB4 PrB4 NdB4 — SmB2 EuB6 GdB2

CeB6 PrB6 NdB6 SmB4 GdB4
Nd2B5 SmB6 GdB6
Sm2B5 Gd2B5
SmB66 GdB66
TbB2 DyB2 HoB2 ErB2 TmB2 YbB2 LuB2
TbB4 DyB4 HoB4 ErB4 TmB4 YbB4 LuB4
TbB6 DyB6 HoB6 ErB12 TmB12 YbB6 LuB12
TbB12 DyB12 HoB12 ErB66 TmB66 YbB12 LuB66
TbB66 DyB66 HoB66 YbB66
438 10 Metal Borides: Versatile Structures and Properties

environmental barrier coatings of turbines. Furthermore, certain representatives

of the metal borides have exceptional special properties. MgB2 is a super-
conductor below its world record TC of 39 K [5a]. TiB2 is a refractory (ceramic)
material with five times higher electrical conductivity than the metal, titanium.
Neodymium iron boride, Nd2Fe14B, is the best hard magnet known so far [6].
Manganese borides may well have potential for magnetocaloric refrigeration [7].
Low thermal conductivities and high Seebeck coefficients of several metal
borides point to potential applications in high-temperature thermoelectric gen-
erators [8]. Chemical properties of the metal borides, on the other hand, seem to
be quite unexplored. Their catalytic properties, for example, still live in a
niche [9]. When talking about boride characteristics, one might also mention
important economical parameters that determine possible uses. Boron itself is
easily available from boric acid and borates, minerals that are not rare and not
extremely expensive. It is also a light element and not described to be toxic, con-
trary to certain boron–oxygen compounds that have been classified by the Euro-
pean Union as very toxic.
The huge variety of boride structures has been described many times and can
be considered textbook knowledge [10,11]. It is reasonable to distinguish
between, on the one hand, the more metal-rich borides in which boron atoms
are either isolated or they form dumbbells or chains (Figure 10.3) and, on the
other side, the boron-rich materials that display very exotic framework struc-
tures, often consisting of beautiful deltahedra (e.g., icosahedron in Figure 10.1).
In between there are the layered structures with two-dimensional arrays of boron
atoms. The degree of dimensionality of the arrangement of the boron atoms cor-
relates closely with the (non)metallic character of the borides. Thus, the struc-
tural diversity is reflected by an extreme variability of electrical properties
between metallic and ceramic. The huge influence of the boron atom structure
on the electronic structure of the metal borides is quite unique and an interesting
topic for research. It has its origin in the special electron-deficient character of
the boron atom that often leads to a very special bonding situation in boron

Figure 10.3 Boron atom arrangement in metallic borides: from isolated boron atoms to dumb-
bells, chains, and layers.
 10.2 Synthesis of Borides 439

compounds. At the same time, the dominance of the boron atom framework
results also in what can be seen as a drawback in the development of new mate-
rials: Simple modifications of existing borides by well-established methods like
doping and substitution are not always possible or do not necessarily lead to the
desired changes in properties. New borides’ existence or characteristics are
mostly unforeseeable, and boride materials cannot often be designed.

10.2
Synthesis of Borides

10.2.1
Powder Preparation

In boride synthesis, due to the refractory character and nonsolubility of both

starting materials and products it is usually the classical solid-state high-temper-
ature reactions (T > 1000 °C) that are chosen to prepare and sinter metal boride
powders, sometimes combined with the application of high pressure. Several
combinations of starting materials are commonly used; most often the direct
combination of the elements themselves (z M + y B → MzBy), but also reactions
between oxides, carbides, halides and hydrogen, carbon, and so on [1–3,12].
Metal oxides can be reduced by boron, carbon, or boron carbide. Boron oxide
can be reduced by metals. Metal halides and boron halides react with hydrogen
(e.g., MCl4 + 2 BCl3 + 5 H2 → MB2 + 10 HCl). Boron halides can also be ther-
mally decomposed. Certain metal halides are also found to react with metal
borides, forming a metathesis product.
Attention has to be paid to the choice of suitable crucible materials, since they
may be found to react with the starting materials, instead of remaining inert.
The following are the examples of boride syntheses [10]:
 Cr + n B → CrBn (1150 °C)
 Sc2O3 + 7 B → 2 ScB2 + 3 BO (1800 °C)
 2 TiCl4 + 4 BCl3 + 10 H2 → 2 TiB2 + 20 HCl (1300 °C)
 n BX3 + (x + 1) M → MBn + x MX3n/x, for example, BCl3 + W → WB + Cl2 + HCl
(H2/1200 °C)
 V2O5 + B2O3 + 8 C → 2 VB + 8 CO (1500 °C)
 Eu2O3 + 3 B4+xC1 x → 2 EuB6 + 3 CO (1600 °C)
 7 Ti + B2O3 + 3 B4+xC1 x → 7 TiB2 + 3 CO (2000 °C)
 3 CaO + 9 B2O3 + 20 Al → 3 CaB6 + 10 Al2O3

10.2.2
Single-Crystal Growth

Small single crystals can be obtained by direct reaction of the elements through
high temperature annealing over long periods of time. The incongruent melting
440 10 Metal Borides: Versatile Structures and Properties

of many borides is challenging, since it may prevent crystallization from melts

and result in the formation of multiphase segregation. Thus, sintering of the sol-
ids is usually preferred to melting the starting materials. But, solid-state
reactions require very high temperatures and extensive reaction times to pro-
duce large single crystals. The floating zone method has been employed success-
fully to synthesize boride crystals of several millimeter lengths [13].
Alternatively, the application of high pressure was proven to yield interesting
results [14]. An important alternative is re-crystallization and synthesis in flux,
using metals such as copper, indium, or aluminum [15].
Occasionally, chemical vapor transport reactions with iodine as transport
agent were used to grow boride crystals [16].

10.2.3
Nanomaterials

There are two major routes that have been developed to synthesize nanoscale
borides [17]: First, alkali metal tetrahydridoborates, such as NaBH4, were used in
solvents (water, organic solvents) to precipitate borides by reduction of metal
salts. Powders produced like this are mostly amorphous, and were originally
used as catalysts without further characterization [9,18]. Today, it is well estab-
lished that nanoscale borides like VB2, TiB2, CrB2, MnB, FeB, Ni3B, and Co2B are
formed at temperatures as low as room temperature and can be crystallized by
annealing at intermediate temperatures [7b,18]. Second, the synthesis in salt
melts has been established and shown to be very successful for the synthesis of
nanoscale metal borides [17,19].

10.3
Metal-Rich Borides: Interstitials or More?

10.3.1
General

The lattices of several of the elemental metals can take up small amounts of
boron. Alloys with boron contents up to 10% are obtained at elevated tempera-
tures and may be retained at room temperature by quenching. This proved suc-
cessful, for example, in the system Ta–B, where body-centered cubic tantalum
and boron form solid solutions with slightly increased lattice parameters a com-
pared to the pure element.
According to Hägg [20], interstitial compounds can be formed at ratios of radii
rB/rM between 0.59 and 0.41, and this requirement is fulfilled by the borides like
Re3B (also nitrides, carbides, etc.). A general phenomenon of the chemistry of
boron-containing metal-rich solids is the variability of the boron atom arrange-
ment – it manifests itself with special evidence in certain binary systems of tran-
sition metals [21]. An example is the Ta–B system [22] with Ta(B), an alloy
 10.3 Metal-Rich Borides: Interstitials or More? 441

Figure 10.4 Coordination sphere of isolated boron atoms (red) in M3B, and structural arrange-
ment of the trigonal prisms (boron atoms: red, metal atoms: gray).

called α-phase in 1949, Ta2B containing isolated B atoms, TaB with zigzag chains
and isostructural to CrB, Ta3B4 with double chains, and TaB2 that contains gra-
phene-like sheets. Ta5B6 (and also Nb5B6) contains double chains, and its struc-
ture type is named after V5B6.

10.3.2
M3B to MB2: From Isolated Boron Atoms to Chains and Sheets

The most common structural motif for the coordination sphere of isolated
boron atoms in metal borides (e.g., Ni3B [18b]) is that of a three-capped trigonal
prism of metal atoms around the boron atom, coordination number 6 + 3 as
shown in Figure 10.4. Typical distances between isolated boron atoms are
around 210 pm.
If one of the rectangular faces of the prism is capped by a boron atom, B–B
dumbbells result. If two are capped by boron atoms instead of metal atoms, a
coordination number of the boron atoms of 6 + 1 + 2 results, and zigzag chains
of boron atoms are formed. Typical distances in B B bonds like this are around
190 pm or smaller. An example is FeB, that crystallizes in the CrB structure
type [23]. If all of the rectangular faces are capped with boron atoms, planar
sheets of boron atoms are formed that are typical for AlB2-type borides. This
structure type will be discussed further (Figure 10.5).

Figure 10.5 Coordination sphere of boron atoms (red) in metal-rich borides.

442 10 Metal Borides: Versatile Structures and Properties

Occasionally, a square antiprism of metal atoms around an isolated boron

atom is found. This results in an unusual coordination number of eight, as seen
for Fe2B [23].

10.3.3
τ-Borides

Borides of the general composition M23B6 are named τ-borides, and more than
80 different compounds have been described, usually being stabilized by a third
component and thus ternary. They crystallize in the face-centered cubic crystal
system with a Cr23C6-type structure and lattice parameters around 1050 pm. An
example of a true binary τ-boride is Co23B6, (Figure 10.6) of which single crystals
were obtained from indium melts [24].

10.3.4
Diborides and Related Compounds

Diborides, MB2, are a striking example for a class of substances with a few exist-
ing but many potential applications. Several of them have outstanding propert-
ies, the most prominent being magnesium diboride, MgB2, a metallic compound
that becomes superconducting below a TC of 39 K, which was a completely
unexpected finding reported in 2001 [5a]. Wires and tapes of several kilometers
in length have since been produced that withstand considerable critical currents,
and prototypes of solenoids and magnetic/medical resonance imaging instru-
ments/imagers were built to demonstrate that this boride may well enter the

Figure 10.6 Crystal structure of Co23B6, a τ-boride.

 10.3 Metal-Rich Borides: Interstitials or More? 443

market as a useful material. A recent world record current for a superconductor

was determined to be 20 kA at 24 K for MgB2 [5b]. Another diboride, TiB2, is
already widely needed. Produced on an industrial scale, mostly in the United
States and Germany, the major part of it ends in vaporization boats for the coat-
ing industry, to produce, for example, metalized bags for potato chips. The basis
of this application is of course the unique profile of properties that titanium
diboride presents: A huge melting point combined with high electrical conduc-
tivity and exceptional chemical inertness.
Historically, probably MgB2 was the first diboride synthesized, since it was
Henry Moissan who obtained a mixture of elemental boron and magnesium
borides when he reduced boron oxide magnesiothermally. It is interesting to
note that the magnesium compound remains the only diboride known until
today for all of the alkali and alkaline earth metals, despite some reports on LiB2
and BeB2 that could not be confirmed.
Diboride structures exhibit a varying stacking of different boron atom layers.
These may be arranged as planar, boat-like, or chair-like condensed six-rings.
Structural motifs emphasizing the coordination of the metal atoms are shown in
Figure 10.7.
The dominant structure type of diborides is named after AlB2, a compound
that was structurally characterized in 1935 and crystallizes in the hexagonal crys-
tal system (Figure 10.8) [25a]. There is one formula unit per unit cell, and the
lattice parameters are around 300 pm, c being about 10% longer than a. It can
be seen that its mean feature are planar sheets of condensed six-rings of boron
atoms, very similar to the arrangement of the carbon atoms in graphite. The
stacking of the layers resembles that in boron nitride.
Thermodynamically stable borides with this structure type are found for many
metals (Mg, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mn, Zr, Al, Mo, Hf, W, Sm, Tm, Er).
Remarkable properties are their conductivities, hardnesses, stability ranges, and
magnetism (e.g., MnB2: ferromagnetic, CrB2: antiferromagnetic). In some cases,
the AlB2-type phases represent the high-temperature modification (WB2), in
others they are metastable and were obtained by ball milling (OsB2) [25b]. ZrB2,
HfB2, NbB2, and TaB2 exhibit melting points >3000 °C, which is high compared
even to the very high melting points of the corresponding metals (Zr: 1857 °C,
Hf: 2222 °C, Nb: 2468 °C, Ta: 2980 °C). TbB2 is ferromagnetic below 151 K and
exhibits relatively strong magnetocrystalline anisotropy.

Figure 10.7 Metal atom coordination in diborides and related compounds.

444 10 Metal Borides: Versatile Structures and Properties

Figure 10.8 AlB2-structure type, space group, P6/mmm (No. 191).

Formally, the bonding situation of MgB2 can be discussed in a Zintl-like man-

ner as a transfer of two electrons per metal atom to the boron atom layers,
resulting formally in 2[B ]1 sheets that are stacked directly above each other
with only weak interactions perpendicular to the layers. However, the transfer of
electrons certainly is not complete and the bonding between M and B is not
predominately ionic. Despite its formal oxidation state of II, the Mg atom shows
a temperature dependence of the electrical conductivity that is typical for a
metal, and X-ray absorption spectroscopic measurements indicated an oxidation
state of the Mg atoms smaller than II. Recently, VB2 was advertised as electrode
component that is extraordinarily redox-active, for example, for energy storage
in redox flow technologies [26].
If the sheets of boron atoms are buckled instead of planar, with sheets of
chair-like, condensed six-rings, the resulting structure type is named after ReB2.
It occurs for Re and Tc, and it is also hexagonal and shown in Figure 10.9(a).

Figure 10.9 ReB2-structure type, space group, P63/mmc (No. 194) (a) and OsB2-structure type,
space group Pmmn (No. 59) (b).
 10.3 Metal-Rich Borides: Interstitials or More? 445

The volume of the unit cell is approximately twice that of the AlB2-type com-
pounds due to the doubled c-axis.
It should be mentioned that ReB2-type crystallizing compounds have been dis-
cussed as superhard and ultraincompressible [4b,27], which is ascribed to a cer-
tain bonding situation with strong metal–boron interactions that have been
characterized being predominately covalent.
The third simple structure type seen for metal diborides is that of OsB2 and
RuB2, exhibiting two-dimensionally linked six-rings in boat-like conformation
(Figure 10.9, b). The crystal system is orthorhombic, and the size of the unit cell is
again approximately twice that of the AlB2-type compounds (a ∼ 300 pm, b ∼ 400
pm, c ∼ 450 pm). Accurate structure data for OsB2 was obtained by neutron diffrac-
tion [28]. Neutron diffraction has been shown to be the appropriate method to
characterize heavy metal borides, but requires the synthesis of isotopic pure (11 B)
samples, since the 10 B isotope absorbs neutrons. The mechanical properties of
OsB2 were described as ultraincompressible but not superhard, again with special
metal–boron interactions between the osmium atom and boron atoms [29].
Several variations of the three structure types already discussed do occur in
metal borides with boron to metal ratios close to two. Thus, a molybdenum
diboride modification (Mo2B4) formally described as “Mo2B5” was found to
exhibit a structure with chair-like and planar B6 rings (Figure 10.10a) [30].

Figure 10.10 Mo2B4, space group, R-3m (No. 166), formerly described as Mo2B5 (a), and Ru2B3
and Os2B3, space group, P63/mmc (No. 194) (b).
446 10 Metal Borides: Versatile Structures and Properties

Neutron diffraction data had to be collected to allow for an explicit assignment

of a correct formula. The scattering power of the light element atoms is insuffi-
cient to determine the location and occupancy of the boron atom sites unambig-
uously next to tungsten or osmium atoms, if X-ray diffraction data is used. The
W analogue is related.
Another variation of the stacking of planar and buckled boron atom layers is
found for Ru2B3 and Os2B3 (Figure 10.10b) [31].

10.4
Boron-Rich Solids

10.4.1
General

The structures of boron and many boron-rich compounds are characterized by

subunits of triangular-defined polyhedra, the so-called deltahedra (from the
Greek letter Δ), for example, octahedra or icosahedra. In the case of closed
polyhedra, one talks of closo-clusters, a nomenclature which makes reference to
the Wade classification used for molecules. These polyhedra – mostly octahedra,
icosahedra, or cube-octahedra – are interconnected either directly or through
additional B–B chains.
Often, but not always it is these polyhedra that are the most striking structural
entities in boron-rich solids. It should be emphasized that the B–B distances
within these polyhedra are usually longer than the ones in between the polyhe-
dra, thus indicating a weaker intrapolyhedral bonding situation compared to the
interpolyhedral interaction [32]. Figure 10.11 shows polyhedra that occur in
binary borides (B6: octahedron, B7: pentagonal bipyramid, B8: dodecahedron,
B12: icosahedron).

10.4.2
Octahedra and Bipyramids in Borides: MB4, MB6, and Na3B20

The aforementioned ThB4 (UB4) structure type contains B6 octahedra and B–B
linkages between them, resulting in heptagone ring as an additional motif

Figure 10.11 Polyhedra in boron-rich borides.

 10.4 Boron-Rich Solids 447

Figure 10.12 Structure type of UB4, space group P4/mbm (No. 127).

(Figure 10.12) [33]. It exists with M = Ce, Gd, U, Th, and La, and a carbon-stabi-
lized variant has been found for Ca.
ErB4, TbB4, and HoB4 have strong anisotropic magnetic properties. Magnetic
structures of MB4 variants have been studied by neutron diffraction, and ErB4
and DyB4 were found to order antiferromagnetically with Néel temperatures of
16 and 21 K, respectively [34]. They crystallize in the UB4 structure type as
explained already, with the orthorhombic Shubnikov space group Pb’am.
The structure type of MB6 is very well known since 1932 [35a]. Hexaborides
crystallize (example EuB6 in Figure 10.13a) in the cubic crystal system (space
group Pm-3m, No. 221). Within this structure, octahedra are three-dimension-
ally interconnected as shown in Figure 10.13(b). Such borides have been

Figure 10.13 Crystals of EuB6 (a) and structure type of CaB6 (b).
448 10 Metal Borides: Versatile Structures and Properties

Figure 10.14 Structure of Na3B20, space group Cmmm (No. 65).

obtained with K, Ca, Sr, Ba, Th, and many lanthanides, and Li2B6 represents a
slightly distorted variant [35b].
The stability, hardness, and good Seebeck coefficients of hexaborides make
them interesting materials for thermoelectric applications [8b]. Further applica-
tions are those of lanthanum hexaboride that is a thermoionic emitter with a
very low work function that can be used as an electrode in transmission electron
microscopes, and especially for electron beam lithography. The properties of
SmB6 were described in 1959 by Samsonov et al. [35c] Recently, this compound
was discussed to be a topological insulator [35d].
Na3B20 is the only boride that contains pentagonal bipyramids and octahedra
(Figure 10.14) [1,36,37]. Originally, it was believed to crystallize with MB6-type
structure, but X-ray and neutron diffraction proved the presence of extra boron
atoms.

10.4.3
Dodecaborides and Borides with Icosahedra

Cube-octahedral entities are found in boron-rich borides such as YB12 and ZrB12
(UB12 structure type, Figure 10.15, a ∼ 740 pm); [38] and further boron-rich
borides show icosahedral entities, for example, Na2B29 (Figure 10.16) [39].
Another binary boride containing B12 units is WB4, which was also found to be
very hard and incompressible [4b].
The UB12 structure was first proposed by Bertaut and Blum [38]. The cube-
octahedral entity of boron atoms forms instead of the icosahedron when M is a
large atomic number element.
As already mentioned, there are numerous examples of the incorporation of
metal atoms in β-B, a process in which the β-B structure is largely preserved.
This is caused by the electron deficit in β-B that has to be compensated in only
partially occupied sites between the linked polyhedra in pure boron by intersti-
tial boron atoms. Structures with 15–16 boron atom positions have been
described. In most cases these phases – as far as they have been discovered and
 10.4 Boron-Rich Solids 449

Figure 10.15 Structure of UB12 with boron atom cube-octahedra, space group Fm-3m (No.
223).

described – are transition metal borides (Cr, Cu, Fe, Mn, Ni, Sc, V, Zn), but
β-rhombohedral boron-type borides of main group metals have been found, too
(Li, Na, Mg, Al).

10.4.4
Carbon-Like Frameworks of Boron Atoms in Borides

For boron-rich borides, the most unusual structure type is that of CrB4, MnB4,
and FeB4. The manganese and chromium variants were synthesized and

Figure 10.16 Structure of Na2B29, space group, Im (No. 8).

450 10 Metal Borides: Versatile Structures and Properties

Figure 10.17 Structure of CrB4 (a), space group, Pnnm (No. 58) and MnB4 (b), space group,
P21/c (No. 14). (Reproduced with permission from Ref. [13]. Copyright 1998, Elsevier.)

structurally described as early as 1968 [40], and since then theoretically investi-
gated many times due to their interesting electronic situation and possible
(super)hardness [41]. Their syntheses, correct structures (Figure 10.17), and
properties were described recently [16,42–46]. The boron atom framework can
be considered to be an electron-deficient variant of the hypothetical tetragonal
diamond, and the boron atoms are indeed coordinated almost tetrahedrally by
four more boron atoms, reminding of sp3-hybridized carbon atoms. In addition
to that, MnB4 exhibits close Mn–Mn contacts indicating a metal–metal multi-
bond caused by a Peierls-type distortion.
The iron variant, FeB4, was first predicted to be stable and superconducting,
and then synthesized at high pressures and found to become superconducting at
low temperatures [46].

10.5
Higher Borides

A vast number of higher, multinary borides have been described [2,47,48]. Inter-
esting examples – double perovskite-like Ti2Rh6B and Ti7Rh4Ir2B8 with a very
unusual planar, isolated B6-ring were published by Fokwa et al. [48,49].

10.6
Conclusion

The synthesis and crystallization of pure borides is challenging, but their bond-
ing situations and crystal structures are fascinating and highly versatile. The cur-
rent state of knowledge shows very interesting chemical and physical properties
 References 451

of borides. But many questions of boride chemistry are still open, and the future
research will certainly prove borides a class of compounds interesting not only
for basic science but also for high-end applications.

References

1 Albert, B. and Hillebrecht, H. (2009) Anorganische Chemie, 4th edn, De

Angew. Chem., Int. Ed., 48, Gruyter, Berlin.
8640–8668. 12 Schwarzkopf, P. and Kieffer, R. (1953)
2 Fokwa, B.P.T. (2014) Encyclopedia of Refractory Hard Metals, Macmillan,
Inorganic and Bioinorganic Chemistry, New York.
John Wiley & Sons, Inc., 1–14. 13 Otani, S., Kosrukova, M.M., and
3 Matkovich, V.I. (1977) Boron and Mitsuhashi, T. (1998) J. Cryst. Growth,
Refractory Borides, Springer, Berlin. 186, 582–586.
4 (a) Aronsson, B., Lundström, T. and 14 (a) Bykova, E., Tsirlin, A.A., Gou, H.,
Rundqvist, S. (1965) Borides, Silicides Dubrovinsky, L., and Dubrovinskaia, N.
and Phosphides, Methuen & Co Ltd, (2014) J. Alloys Comp., 608, 69–72;
London; (b) Yeung, M.T., Mohammadi, (b) Gou, H., Dubrovinskaia, N., Bykova, E.,
R. and Kaner, R.B. (2016) Annu. Rev. Tsirilin, A., Kasinathan, D., Schnelle, W.,
Mater. Res., 46, 465–485. Richter, A., Merlini, M., Hanfland, M.,
5 (a) Nagamatsu, J., Nakagawa, N., Abakumov, A.M., Batuk, D., Van
Muranaka, T., Zentani, Y., and Akimitsu, J. Tendeloo, G., Nakajima, Y., Kolmogorov,
(2001) Nature, 410, 63–64; (b) Del Rosso, A., and Dobrovinsky, L. (2013) Phys. Rev.
A. (2014 CERN document server, April 14, Lett., 111 157002.
2014. 15 (a) Higashi, I., Takahashi, Y. and Atoda, T.
6 Herbst, J.F., Lee, R.W., and Pinkerton, F.E. (1977) J. Cryst. Growth, 33, 207–211;
(1986) Annu. Rev. Mater. Sci., 16, (b) Sinel’nikova, V.S., Gurin, V.N.,
467–458. Pilyankevich, A.N., Strashinskaya, L.V.,
7 (a) Fries, M., Gercsi, Z., Ener, S., Skokov, and Korsukova, M.M. (1976) J. Less-
K.P., and Gutfleisch, O. (2016) Acta Common Met., 46, 265–272; (c) Vojteer,
Mater., 113, 213e220; (b) Klemenz, S., N., Schroeder, M., Röhr, C., and
Fries, M., Dürrschnabel, M., Skokov, K., Hillebrecht, H. (2008) Chem. Eur. J., 14,
Kleebe, H.-J., Gutfleisch, O., and Albert, 7331–7342; (d) Amsler, B., Fisk, Z., Sarrao,
B., submitted. J.L., Molnar, S.von., Meisel, M.W., and
8 (a) Mori, T. and Nishimura, T. (2006) Sharifi, F. (1998) Phys. Rev. B 57
J. Solid State Sci., 179, 2908–2915; 8747–8750.
(b) Gürsoy, M., Takeda, M., and Albert, B. 16 (a) Knappschneider, A., Litterscheid, C.,
(2015) J. Solid State Chem., 221, Kurzman, J., Seshadri, R., and Albert, B.
191–195; (c) Gürsoy, M., Hempel, S., (2011) Inorg. Chem., 50, 10540–10542;
Reitz, A., Hofmann, K., and Albert, B. (b) Knappschneider, A., Litterscheid, C.,
(2014) Z. Anorg. Allg.Chem., 640, George, N.C., Brgoch, J., Wagner, N., Beck,
2714–2716. J., Kurzman, J.A., Seshadri, R., and Albert,
9 Schlesinger, H.I., Brown, H.C., Finholt, B. (2014) Angew. Chem., Int. Ed., 126,
A.E., Gilbreath, J.R., Hockstra, H.R., and 1710–1714.
Hyde, E.K. (1953) J. Am. Chem. Soc., 75, 17 Carenco, S., Portehault, D., Boissière, C.,
215–219. Mézailles, N., and Sanchez, C. (2013)
10 Greenwood, N.N. and Earnshaw, A. (1988) Chem. Rev., 113 (10), 7981–8065.
Chemie der Elemente, 1st edn, Wiley-VCH 18 (a) Glavee, G.N., Klabunde, K.J., Sorensen,
Verlag GmbH, Weinheim. C.M., and Hadjipanayis, G.C. (1993) Inorg.
11 Janiak, C., Meyer, H.-J., Gudat, D., and Chem., 32, 474–477; (b) Kapfenberger, C.,
Alsfasser, R. (2012) Riedel Moderne Hofmann, K. and Albert, B. (2003) Solid
452 10 Metal Borides: Versatile Structures and Properties

State Sci., 5, 925–930; (c) Hofmann, K., 29 (a) Chung, H.-Y., Weinberger, M.B.,
Kalyon, N., Kapfenberger, C., Lamontagne, Levine, J.B., Kavner, A., Yang, J.-M.,
L., Zarrini, S., Berger, R., Seshadri, R., and Tolbert, S.H., and Kaner, R.B. (2007)
Albert, B. (2015) Inorg. Chem., 54, Science, 316, 436–439; (b) Kaner, R.B.,
10873–10877; (d) Rades, S., Kornowski, A., Gilman, J.J. and Tolbert, S.H. (2005)
Weller, H., and Albert, B. (2011) Science, 308, 1268–1269.
ChemPhysChem, 12, 1756–60; (e) Rades, 30 (a) Froscher, M., Klein, W., Bauer, J., Fang,
S., Kraemer, S., Seshadri, R., and Albert, B. C., Halet, J.-F., Senyshyn, A., Baehtz, C.,
(2014) Chem. Mater., 26 1549–1552. and Albert, B. (2007) Z. Anorg. Allg.
19 (a) Portehault, D., Devi, S., Beaunier, P., Chem., 633, 2626; (b) Kayhan, M.,
Gervais, C., Giordano, C., Sanchez, C., and Hildebrand, E., Frotscher, M., Senyshyn,
Antonietti, M. (2011) Angew. Chem., Int. A., Hofmann, K., Alff, L., and Albert, B.
Ed., 50, 3262–3265; (b) Terlan, B., Levin, (2012) Solid State Sci., 14, 1656.
A.A., Börnert, F., Simon, F., Oschatz, M., 31 Frotscher, M., Senyshyn, A., and Albert, B.
Schmidt, M., Cardoso-Gil, R., Lorenz, T., (2012) Z. Anorg. Allg. Chem.,
Baburin, I.A., Joswig, J.-O., and 638, 2978.
Eychmüller, A. (2015) Chem. Mater., 27, 32 Albert, B. (2001) Eur. J. Inorg. Chem.,
5106–5115; (c) Terlan, B., Levin, A.A., 1679.
Börrnert, F., Zeisner, J., Kataev, V., 33 Zalkin, A. and Templeton, D.H. (1950)
Schmidt, M., and Eychmüller, A. (2016) J. Chem. Phys., 18, 391–392.
Eur. Inorg. Chem., 3460–3468. 34 Gianduzzo, J.C., Georges, R., Chevalier, B.,
20 Hägg, G. (1931) Z. Phys. Chem., B12, 33. Etourneau, J., Hagenmuller, P., Will, G.,
21 Greenwood, N.N., Parish, R.V., and and Schäfer, W. (1981) J. Less-Comm.
Thornton, P. (1966) Chem. Soc. Q. Rev., Met., 82, 29–35.
20, 441–464. 35 (a) von Stackelberg, M. and Neumann, F.
22 (a) Kiessling, R. (1949) Acta Chem. Scand., (1932) Z. Phys. Chem., 19, 314–320;
3, 603–615; (b) Bolmgren, H., Lundström, (b) von Schnering, H.G., Mair, G., Woerle,
T., Tergenius, L.-E., Okada, S., and M., Nesper, R., and Anorg, Z. (1999) Allg.
Higashi, I. (1990) J. Less-Comm. Met., 161, Chem., 625, 1207–1211; (c) Samsonov,
341–345. G.V., Zhuravlev, N.N., Paderno, Yu.B., and
23 Kapfenberger, C., Albert, B., Pöttgen, R., Melik-Adamyan, V.R. (1959)
and Huppertz, H. (2006) Z. für Kristallogr., Kristallografiya, 4, 538–541 (english
221, 477–481. translation: Sov. Phys. Crystallogr. 1959, 4,
24 Kotzott, D., Ade, M., and Hillebrecht, H. 507–509); (d) Kim, D.J., Xia, J. and Fisk, Z.
(2009) J. Solid State Chem., 182, (2014) Nat. Mater., 13, 466–470.
538–546. 36 Albert, B. (1998) Angew. Chem., Int. Ed.,
25 (a) Hofmann, W. and Jäniche, W. (1935) 37, 1117.
Naturwiss, 23, 851; (b) Xie, Z., Graule, M., 37 Albert, B. and Hofmann, K. (1999) Z.
Orlovskaya, N., Payzant, E.A., Cullen, D.A., Anorg. Allg. Chem., 625, 709.
and Blair, R.G. (2014) J. Solid State Chem., 38 Bertaut, F. and Blum, P. (1949) C. R. Acad.
215, 16–21. Sci. Paris, 229, 666–667.
26 (a) Licht, S., Wu, H., Yu, X., and Wang, Y. 39 Albert, B., Hofmann, K., Fild, C., Eckert,
(2008) Chem. Commun., 3257–3259; H., Schleifer, M., and Gruehn, R. (2000)
(b) Stuart, J., Hohenadel, A., Li, X., Xiao, Chem. Eur. J., 6, 2531–2536.
H., Parkey, J., Rhodes, C.P., and Licht, S. 40 Andersson, S. and Lundstroem, T. (1968)
(2015) J. Electrochem. Soc., 162, Acta Chem. Scand., 22, 3103–3110.
A192–A197. 41 Burdett, J.K. and Canadell, E. (1988) Inorg.
27 Cumberland, R.W., Weinberger, M.B., Chem., 27, 4437–4444.
Gilman, J.J., Clark, S.M., Tolbert, S.H., and 42 Knappschneider, A., Litterscheid, C.,
Kaner, R.B. (2005) J. Am. Chem. Soc., 127, Dzivenko, D., Kurzman, J., Seshadri, R.,
7264–7265. Wagner, N., Beck, J., Riedel, R.,
28 Frotscher, M., Hölzl, M., and Albert, B. and Albert, B. (2013) Inorg. Chem., 52,
(2010) Z. Anorg. Allg. Chem., 636, 1783. 540–542.
 References 453

43 Niu, H., Wang, J., Chen, X.-Q., Li, D., Li, 46 Gou, H., Dubrovinskaia, N., Bykova, E.,
Y., Lazar, P., Podloucky, R., and Tsirilin, A., Kasinathan, D., Schnelle, W.,
Kolmogorov, A.N. (2012) Phys. Rev. B, 85, Richter, A., Merlini, M., Hanfland, M.,
144116. Abakumov, A.M., Batuk, D., Van
44 Knappschneider, A., Litterscheid, C., Tendeloo, G., Nakajima, Y., Kolmogorov,
Brgoch, J., George, N.C., Henke, S., A., and Dobrovinsky, L. (2013) Phys. Rev.
Cheetham, A.K., Hu, J.G., Seshadri, R., and Lett., 111 157002.
Albert, B. (2015) Chem. Eur. J., 21, 47 Mori, T. (2008) Handbook on the Physics
8177–8181. and Chemistry of Rare-Earths, vol. 38 (eds
45 Gou, H., Tsirlin, A.A., Bykova, E., K.A. Gschneider Jr, J.-C. Bunzli, and V.
Abakumov, A.M., Tendeloo, G.Van., Pecharsky), North-Holland, Amsterdam.
Richter, A., Ovsyannikov, S.V., Kurnosov, 48 Fokwa, B.P.T. (2010) Eur J. Inorg. Chem.,
A.V., Trots, D.M., Konôpková, Z., 3075.
Liermann, H.-P., Dubrovinsky, L., and 49 Fokwa, B.P.T. and Hermus, M. (2012)
Dubrovinskaia, N. (2014) Phys. Rev. B, 89, Angew. Chem., Int. Ed., 51, 1702–1705.
064108.