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Beryllium bis(diazaborolyl): old neighbors finally

shake hands
T. Arnold, H. Braunschweig,* W. C. Ewing, T. Kramer, J. Mies and J. K. Schuster

Published on 11 November 2014. Downloaded on 25/11/2014 09:28:23.

Received 28th October 2014,

Accepted 5th November 2014
DOI: 10.1039/c4cc08519a
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The synthesis of a linear beryllium bis(diazaborolyl) compound featuring

the first non-cluster bond between boron and beryllium has been
achieved through the reaction of Yamashitas lithium diazaborolide
and BeCl2. In accord with the established chemistry of beryllium, the
bonding is polar covalent in character, as determined by structural
and spectroscopic analysis, as well as reactivity studies.

The formation of bonds between nucleophiles and electrophiles lies

at the very core of our understanding of chemical bonding. In most
cases, these two classes of compounds are separated by electronegativity dierences, with the electron density of the nucleophile
attributable to its larger electronegativity, and the electron-deficiency
of the electrophile resulting from its electropositive nature. The
capacity of the comparatively electronegative elements from the
top-right corner of the periodic table (Fig. 1, shaded in blue)
to behave as nucleophiles facilitates their use in bond-forming
reactions. Heteroatomic 2-center/2-electron bonds between electropositive elements are comparatively rare, in large part because it is
not trivial to induce an electropositive element to take on the excess
electron density required for nucleophilic behavior.
Among the comparatively less electronegative elements of
the periodic table, boron has shown a pronounced capacity to
act as a nucleophile if properly induced. Though the field is still
relatively young, examples of nucleophilic boron have emerged
including base-stabilized boroles,1 unsymmetrically-substituted
diboron compounds,2 pinocolatoboryl cuprates3 and an anionic
dimetalloborylene.4 The most versatile and widely used boron
nucleophile is the 1,3,2-diazaborolide anion.5 Since the initial
synthesis of the anion as a convenient lithium salt by Yamashita
and Nozaki6 these compounds have provided a starting point for
a large range of reactions utilizing boron as a nucleophile. Fig. 1
depicts the breadth of use of Yamashitas anion in facilitating
r Anorganische Chemie, Julius-Maximilians-Universita
t Wu
rzburg,
Institut fu
rzburg, Germany. E-mail: h.braunschweig@uni-wuerzburg.de
Am Hubland, 97074 Wu
Electronic supplementary information (ESI) available: All synthetic, spectroscopic and computational details. CCDC 1018058 and 1018059. For ESI and
crystallographic data in CIF or other electronic format see DOI: 10.1039/
c4cc08519a

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Fig. 1 Schematic of the compounds known between main group elements and 1,3,2-diazaborolyls. Original references are as follows: I;6 II, III;8
IV;9 V;10 VI, VII;11,12 VIII;13,14 IX;15 X, XI.13,16

the formation of bonds between boron and other electropositive

members of the main group.7 The coverage of the p-block is
extensive, and is supplemented by examples of bonding to the
Group 12 post-transition-metals (VIII) and to s-block elements in
the form of the aforementioned lithium diazaborolide (I), as well
as magnesium mono- and bis-diazaborolide complexes (II, III).
As may be noted from Fig. 1, bonding between the diazaborolide
anion and beryllium is presently unknown. In fact, a survey of

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the literature returns examples of bulk material phases containing

the two elements, inclusion of beryllium in polyhedral borane and
carborane clusters,17 and hydride-bridged BeHB complexes,18 but
despite berylliums known tendency to form bonds with covalent
character19 and the similarities in the sizes of the two atoms, no
examples of classical non-cluster bonding between the two atoms
in isolated molecules are found. It is undoubtedly the toxicity of
beryllium and the precautions required for its safe use which
have historically limited the exploration of its chemistry, thereby
explaining the absence of examples of BBe bonding despite the
otherwise-extensive employment of the 1,3,2-diazaborolide
anion across the main group.
Bonds between beryllium and the isoelectronic/isostructural
congeners of the 1,3,2-diazaborolide anion, neutral N-heterocyclic
carbenes (NHCs), have been known for a number of years.20 The
syntheses of these compounds were carried out through simple
complexation of NHCs to BeCl2 or BeR2, with the retention of at least
one of the original substituents on beryllium (Scheme 1). In contrast,
when we reacted two equivalents of the aforementioned lithium
diazaborolide with BeCl2 in benzene, beryllium bis(diazaborolyl) 1
was formed with the concomitant elimination of LiCl (Scheme 1,
eqn (4)). Filtration of the solution, followed by evaporation of
the benzene and recrystallization from cold hexane ( 30 1C) gave
analytically pure 1 in 70% yield.
The 9Be NMR spectrum of 1 features a broad peak at 44 ppm,
significantly outside the normal range for two-coordinate
beryllium.21 Despite the fact that this peak represents the
lowest-field 9Be NMR resonance yet reported, the downfield
position was reassuringly predicted by DFT/GIAO calculations

Scheme 1 Syntheses of NHC-beryllium and beryllium bis(diazaborolyl)

complexes. Eqn (1), ref. 20d; eqn (2), ref. 20a; eqn (3a), ref. 20c; eqn (3b),
ref. 20b; Dip = 2,6-diisopropylphenyl, iPr = isopropyl.

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(44 ppm, B3LYP/6-311 + G(2d,p)) and the exceptional broadness

of the peak (FWHH = B1200 Hz) is consistent with the placement of the 9Be nucleus between two quadrupolar 11B nuclei.
The 11B NMR spectrum shows a broad peak at 28 ppm, falling in
an appropriate range for a 1,3,2-diazaborolyl complex.5b The
1
H NMR spectrum indicates equivalence of the borolyl ligands,
and lacks the peaks attributable to bound solvent molecules
known to accompany IIII.
A single-crystal X-ray study confirmed the identity of 1
(Fig. 2). The BBe bonds were determined to measure
1.870(3) and 1.873(3) , which fit nicely between the lengths
of the BLi bond in I (2.291(6) )6 and BB bonds (1.707(6) ,
1.729(6) ) in IV (X = Cl).13 Unlike its group 2 cousin II,8 1 is
linear, with a central BBeB angle of 177.7(14)1, which, along
with the lack of coordinated solvent molecules, causes 1 to
more closely resemble the structures of the bis(diazaborolyl)
complexes of the post-transition-metals of group 12 (VIII).22
The DFT optimized geometry of 1 (B3LYP/6-311G(d)) closely
matches the experimentally determined structural parameters
(coordinates given in Table S1, ESI).
The greater capacity of beryllium to participate in covalent
bonding, as compared to the remainder of the alkaline earth
metals, is well known19 and both the structural and spectroscopic properties of 1 indicate the presence of highly polar
covalent bonds between boron and beryllium. Table 1 compares
the lengths of the BN bonds, the NBN angles, and the 11B
NMR shifts of 1, I, II, and IV-Cl along with the protonated
diazaborole [(HCN(dipp))2B]H (2) and values calculated for
the naked diazaborolide anion [(HCN(dipp))2B] (XII).23 As the
character of the diazaborolyl progresses from purely anionic, as
epitomized by the naked anion, to a participant in a covalent
bond with presumably less strict anionic character, the BN
lengths in the diazaborolyl ring are observed to contract, while

Fig. 2 Crystallographically determined structure of 1. Ellipsoids represent

50% probability and have been omitted from the dipp moieties of the
1,3,2-diazaborolyl ligands for clarity. All hydrogen atoms have been omitted
likewise. Selected bond lengths () and angles (1): BeB, 1.870(3), 1.873(3);
BN, 1.447(2), 1.450(2), 1.449(2), 1.449(2); NBN, 101.9(1), 101.9(1);
B1BeB2, 177.7(1).

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Table 1 Comparison of the BN bond lengths, the BNB angles and

11
B NMR shifts of relevant diazaboroles, diazaborolides and diazaborolyls

Compounda

BN (, avg.)

BNB (1)

11

XII
I
II
1
IV-Cl

1.475
1.466
1.479
1.449
1.452

57b
45
38
28
25

1.421

97.7
99.2(2)
99.3(3)
101.9(1)
103.0(3)
102.5(3)
105.3(2)

B NMR (ppm)

23

Published on 11 November 2014. Downloaded on 25/11/2014 09:28:23.

For references see Fig. 1 (caption). Geometry optimized and NMR

shift calculated at the B3LYP/6-311G(d) level.

the NBN angles become less acute. These lengths and angles
in 1 fit between those of the highly ionic diazaborolides (I and II)
and the substantially less polarized diazaborole 2, and are quite
similar to those found in the triborane species IV-Cl. The
11
B NMR shift of the diazaborolyl-boron is likewise a useful indicator
of covalency, as strong ionic character has been shown to result
in a downfield shift of the observed resonance.24 Here again, the
11
B NMR resonance of 1 falls between those of the highly ionic
compounds and those of more purely covalent species.
The strongly polar-covalent nature of the bonding between
the borolyl and beryllium is illustrated by examination of the
NPA charges in 1, which indicate a positively-charged beryllium
center, flanked by nearly-neutral boron atoms, oset by large
negative charges on the four nitrogen atoms of the diazaborolylrings (Scheme 2). The positive charge on beryllium is reflected in
its reactivity. Methanolysis of 1 cleanly aorded the protonated
diazaborole 2, along with insoluble materials presumed to be the
polymeric beryllium methanolate,25 while an equivalent reaction
with d4-methanol cleanly gave the 2-D-diazaborole (comparison
of spectra in Fig. S5 and S6, ESI).
Further demonstrating the electrophilic nature of the
beryllium atom in 1, reaction of 1 with one equivalent of the
NHC 1,3-dimethylimidazol-2-ylidene (IMe) eected addition at
the beryllium to yield the trigonal mixed-base adduct (3), which
was isolated by slow crystallization from benzene. The 9Be NMR
spectrum of 3 showed a broad peak at 28 ppm, while the 11B NMR

Fig. 3 Crystallographically determined structure of 3. Ellipsoids represent

50% probability and have been omitted from the dipp moieties of the
1,3,2-diazaborolyl ligands for clarity. All hydrogen atoms have been omitted
likewise. Selected bond lengths () and angles (1): BeB, 1.944(3), 1.954(3);
BN, 1.471(3), 1.471(3), 1.467(3), 1.474(3); C7Be, 1.781(3), C7N, 1.353(2),
1.355(3); B1BeB2, 132.82(16); NBN, 100.6(2), 100.5(2).

resonance shifted downfield to 38 ppm. This shift in the 11B

spectrum indicates an increase in ionic character of the BeB
bond, likely the result of the more electron rich beryllium
center, and the less-effective orbital overlap resulting from
the increased BeB bond lengths (see below) necessary to
accommodate the increased steric requirements of the system.
The solid state structure of 3 was determined via single crystal
X-ray crystallography (Fig. 3). In 3, the BeB bonds stretch to
1.944(3) and 1.954(3) to allow space for the increased steric
bulk at beryllium. The central beryllium atom features a planar
geometry, with bond angles summing to 3601. The bond between
the carbene and beryllium measures 1.781(3) , which is shorter
than the BeC bonds in the tri-NHC-substituted tetrahedral cation
[Be(IMe)3Cl]+ (1.807(3) , 1.822(3) ),20a in the same range as the
bond in IDipBeCl2 (1.773(5) , IDip = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene),20d and slightly longer than the bond in
IDipBe(BH4)2 (1.765(5) ).20d
In conclusion, we herein report the synthesis of a beryllium
bis(diazaborolyl) compound containing the first example of a
non-cluster bond between boron and beryllium. Structural and
spectroscopic analysis of this compound indicate that the bonding
between the boron and beryllium is polar-covalent in nature, which
stands in juxtaposition against the more purely ionic bonding
featured between Yamashitas anion and other s-block elements.
Charge analysis and reactivity studies demonstrated the electrophilicity of the Be atom in the highly polarized BeB bond.
The authors wish to gratefully acknowledge financial support
from the Deutsche Forschungsgemeinschaft (DFG).

Notes and references

Scheme 2 The reactivity of bis(diazaborolyl) beryllium 1. The NPA
charges given on the drawing of 1 were calculated at the B3LYP/6311G(d) level of theory.

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