Behavior of dodecahydro-closo-dodecaborate anion B12H 12 2- in reaction with Au(Ph3P)Cl

Article abstract of DOI:10.1134/S003602361104005X

The reaction of the anion B₁₂H ₁₂ ^2- with [Au(Ph₃P)Cl] in acetonitrile was studied. The nature of the initial cation of the closo-dodecaborate and the reagent ratio was shown to affect complexing. The X-ray structures of compounds Au(Ph₃P) ₂[AgB₁₂H₁₂] (I) and [Au₉(Ph ₃P)₈]B₂₄H₂₃ (II) were determined. Complex I is the first example where B₁₂H ₁₂ ^2- is coordinated to silver(I) atoms in the face coordination mode. In complex II, B₁₂H ₁₂ ^2- is oxidized to the dimeric trianion B₂₄H ₂₃ ^3- where the two icosahedra are linked by a B-H-B′ bridge.

Full text of DOI:10.1134/S003602361104005X

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2011, Vol. 56, No. 4, pp. 524–529. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.V. Avdeeva, E.A. Malinina, O.N. Belousova, L.V. Goeva, I.N. Polyakova, N.T. Kuznetsov, 2011, published in Zhurnal Neorganicheskoi Khimii, 2011,
Vol. 56, No. 4, pp. 564–569.
COORDINATION
COMPOUNDS
Behavior of Dodecahydroꢀclosoꢀdodecaborate Anion
2
−
В Н in Reaction with Au(Ph P)Cl
1
2 12
3
V. V. Avdeeva, E. A. Malinina, O. N. Belousova, L. V. Goeva, I. N. Polyakova, and N. T. Kuznetsov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
Received November 18, 2009
2
−
Abstract—The reaction of the anion В Н with [Au(Ph P)Cl] in acetonitrile was studied. The nature of the
1
2
12
3
initial cation of the closoꢀdodecaborate and the reagent ratio was shown to affect complexing. The Xꢀray
structures of compounds Au(Ph P) [AgB H ] ( and [Au (Ph P) ]B H II were determined. Complex
I
)
( )
24 23
3
2
12 12
9
3
8
2
−
I
is the first example where В Н is coordinated to silver(I) atoms in the face coordination mode. In comꢀ
12 12
2
−
3−
plex II, В Н is oxidized to the dimeric trianion В Н , where the two icosahedra are linked by a B–H–B'
12 12 24 23
bridge.
DOI: 10.1134/S003602361104005X
The documentation concerning the coordination tively [9]. Here, we study the reaction of closoꢀdodeꢀ
2
n
−
2−
chemistry of cluster boron anions B H (where
n
=
caborate anion В Н with Au(Ph P)Cl in acetoniꢀ
12 12
3
n
1
0, 12) implies that not only these electronꢀdeficient trile, study the effect of the nature of the cation on the
compounds having low donating capacities [1] are initial closoꢀdodecaborate and the reagent ratio on the
coordinated to metal atoms, but they also show a great product composition, and solve the structure of the
variety of types of bonding to the metal in coordinaꢀ products.
tion compounds. In copper(I) and silver(I) comꢀ
plexes, for example, the closoꢀdodecaborate anion was
EXPERIMENTAL
Syntheses
shown to be capable of forming metal complexes
2
−
where В Н is involved in the inner coordination
1
2
12
sphere via forming 3с2е (MHB) bonds with metal
atoms [2–5] in the same manner as the closoꢀdecaboꢀ
rate anion is [6].
Dodecahydroꢀclosoꢀdodecaboratosilver(I) [Ag B H ]
2
12 12
was prepared according to [10].
Chloro(triphenylphosphine)gold(I) Au(Ph P)Cl
3
Only one gold compound with closoꢀhexaborate anion
was prepared by reacting [HAuCl4] with Ph3P as
described elsewhere [11].
2
−
В Н6 , having the composition [Au (Ph P) (B Н )] was
6
2
3
2
6
6
Bis(triphenylphosphine)gold(I) catenaꢀ( 2
µ
ꢀdodecahyꢀ
described [7, 8]; this compound was prepared by the
reaction
droꢀclosoꢀdodecaborate {(Au(Ph P) )(AgB H )} (I). To
3
2
12 12 n
a solution containing 0.1 mol of Au(Ph P)Cl in acetoꢀ
nitrile + benzene (20 mL), added was a solution of
3
(
Bu N
)
B Н + 2Au
(
Ph3P
)
Cl
4
6
6
2
(
1)
0
.1 mole of [Аg В Н12] in 20 mL of acetonitrile. The
→
[
Au
(
Ph
P
)
B
Н
6
)
]
(
III
)
+ 2 Bu
(
N
)
Cl.
2 12
2
3
6
4
2
2
−
+
Au to В Н ratio in the reaction mixture was 1 : 1.
1
2
12
Each Au(I) atom in compound III is linked to the
triangular face В3 of the closoꢀhexaborate anion and
the phosphorus atom of triphenylphosphine. The terꢀ
minal hydrogen atoms are presumably uninvolved in
gold coordination [7, 8] The IR spectrum of comꢀ
The resulting clear reaction solution was allowed to
stand in the dark for 12 h. Crystals of prismatic habit
were forming upon isothermal evaporation of solvents.
Yield of compound I was about 80%.
–
1
Octakis(triphenylphosphine)nonagold(I) tricosahyꢀ
pound III features an absorption band at 2473 cm
associated with the bending vibrations of pendant
drotetracosaborate [Au (Ph P) ]B H (II). To a
9
3
8
24 23
solution of 0.1 mole of [Аg В Н12] in 20 mL of acetoꢀ
2
12
2
−
B⎯H bonds in В Н .
6 6
nitrile, added was a solution of Au(Ph P)Cl, taken in an
3
2
10
−
excess, in acetonitrile + benzene (20 mL). After the
reagents were combined, a white precipitate (AgCl)
was gradually forming. The reaction solution was
Our preliminary studies of reactions of В Н and
10
2
−
В Н with Au(Ph P)Cl allowed us to isolate the comꢀ
1
2
12
3
plex [1ꢀ(Au (Ph P) )В Н9] and complex II, respecꢀ allowed to stand in the dark for 5 h. Lightꢀorange crysꢀ
3
3
3
10
524

BEHAVIOR OF DODECAHYDROꢀclosoꢀDODECABORATE
525
tals of prismatic habit coated with a reduced finely Table 1. Selected crystallographic data, details of experiment,
and refinement factors for compounds I and II
divided silver layer were isolated from the reaction
mixture. The yield of compound II did not exceed
50%.
Parameter
I
II
Formula weight
Crystal system
971.19
2070.19
Elemental Analyses
Analysis for carbon and hydrogen was carried out
Monoclinic
Monoclinic
on a CHINSꢀ3 FA 1108 Elemental Analyzer (Carlo Space group
,
Z
P
2 /
1
c, 4
C2/c, 8
Erba). Boron was determined by atomic absorption
spectroscopy on PerkinElmer spectrophotometers
model 2100 equipped with an HGAꢀ700 electrotherꢀ
mal atomizer [12]. Silver and gold were determined on
AASꢀ303 in acetylene–air flame.
a
, Å
, Å
12.711(3)
23.256(4)
14.759(4)
104.99(2)
4214.4(17)
1.531
30.556(3)
16.1407(16)
32.958(3)
116.646(2)
14528(2)
1.893
b
c
, Å
, deg
, Å3
For C H AgAuB P anal. calcd., %: H, 4.95; B,
36
48
12
2
β
1
4
6
4
3.27; C, 44.24; Ag, 11.04; Au, 20.15.
V
ρ
μ
For compound found, %: H 4.78; B 12.58; C
I
4.12; Ag, 10.69; Au, 20.08.
, g/cm3
calc
For C H Au B P anal. calcd., %: H, 4.03; B,
144 167
9 24 8
, mm–1
Mo
4.043
9.187
.21; C, 41.40; Au, 42.43.
For compound II found, %: H, 3.91; B, 6.12; C,
1.10; Au, 42.24.
Crystal size, mm
θ range, deg
0.45
×
0.30
×
0.22 0.30
×
0.25
×
0.10
1.75 <
θ
< 27.00 1.76 <
θ
< 24.00
IR Spectra
Number of reflections
IR spectra for compounds
Nujol mulls on an Infralum FTꢀ02 (Lumex) spectroꢀ
I
and II were recorded as measured
11311
9190 [0.0347]
6527
53017
11310 [0.1687]
3889
–1
unique
(N) [Rint]
photometer in the range 600–4000 cm with resoluꢀ
–1
tion of 1 cm .
For compound
observed
(
I
> 2σ(I))
I:
ν
(B1 H) 2475;
ν
(BH)MHB 2342,
(
No)
–
2
150;
δ
(BBH) 1070 cm .
GOOF
1.016
0.774
For compound II
:
ν
(BH) 2515; ν(BH)BHB 1875;
–1
δ
(BBH) 1054 cm .
R
R
1, wR2 for No
1, wR2 for
0.0617, 0.1570
0.0918, 0.1833
1.522/–2.715
0.0461, 0.0663
0.1719, 0.0843
1.432/–1.065
N
11B NMR Spectra
11B NMR spectra of solutions of complexes
Δρmax/Δρ , e/Å3
min
I
and II
in acetonitrile were recorded on a Bruker AC 200
spectrometer at a frequency of 64.297 MHz with interꢀ
nal deuterium stabilization relative to external boron
trifluoride etherate. B NMR data for complex II are
found in [9].
The coordinates of H atoms of Ph3P molecules were
calculated. All H atoms were refined using the rider
model with isotropic thermal parameters as Uj(H) =
11
1.2Ueq of the relevant nonꢀhydrogen atom. The leastꢀ
squares fits were carried out using software
SHELXL97 [17]. Selected crystallographic data for
Xꢀray Crystallography
compounds I and II, the parameters of the Xꢀray difꢀ
Diffraction intensity arrays were obtained from
fraction experiment, and structure refinement paramꢀ
eters are listed in Table 1; some bond lengths and bond
angles are found in Table 2.
crystals of complexes
Bruker AXS SMART 1000 automated diffractometers
Mo , graphite monochromator, scans) at 297(2)
and 120(2) K, respectively. Program packages
XSCANS [13] (for complex
) and SMART and been deposited with the Cambridge Structural Dataꢀ
SAINT [14] (for complex II) were used in collecting base (CCDC No. 723647). Data for compound II are
I and II on Bruker AXS P4 and
(
λ
K
ω
α
The crystallographic data for compound
I have
I
and processing I(hkl)
data sets. The correction for available from the Cambridge Structural Database
absorption was applied using the MULTISCAN (Refcode KIYZAU).
method [15, 16]. The structures were solved by a direct
method (SHELXS97 [17]). Nonꢀhydrogen atoms
RESULTS AND DISCUSSION
A method for preparing a gold(I) complex of the
(Ph P) (B ] by reacꢀ
were refined in the anisotropic approximation. The
positions of the H atoms of polyhedral anions were
found from difference synthesizes and then idealized. closoꢀhexaborate anion [Au
Н )
6 6
2
3
2
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 4 2011

526
AVDEEVA et al.
Table 2. Selected bond lengths (d) and bond angles (ω) in the
structure of complex I
[
Ag B Н
]
+ 9Au
(
Ph3P
)
Cl
2
12 12
(4)
0
→
AgCl Ag ↓ + Au Ph P В Н II .
[
(
) 24 23 ( )
]
(
)
9
3
8
Bond
d, Å
For the equimolar reagent ratio, AgCl was not
formed, and the combination of physicochemical
methods allowed us to identify the reaction product
Au(1)–P(1)
2.338(2)
2.3405(19)
2.09
Au(1)–P(2)
Ag(1)–H(12)#1
Ag(1)–H(10)#1
Ag(1)–H(9)#1
Ag(1)–B(1)
with compound
showed both silver(I) and gold(I) atoms in complex
In the IR spectrum of compound , in the region of the
boron–hydrogen stretches there are a strong band (ВН)
due to “free” BH groups at 2475 cm and two broadꢀ
I (Scheme 3). Elemental analysis
I.
2.29
I
2.49
ν
2.498(11)
2.528(11)
2.614(11)
2.630(13)
2.738(11)
1.95
–1
–1
Ag(1)–B(12)#1
Ag(1)–B(10)#1
Ag(1)–B(2)
ened mediumꢀintensity bands (~2342 and 2150 cm ),
which are associated with the stretching vibrations
ν
(ВН)MHB. A similar pattern is observed in the IR
spectra of Cat[AgB H ] anionic complexes [4]. In the
12
12
Ag(1)–B(9)#1
Ag(1)–H(1)
region where the vibrations of phenyl rings of tripheꢀ
–1
nylphosphine molecules appear (600–1600 cm ), the
IR spectrum of complex is an analogue of the specꢀ
trum of the precursor Au(Ph P)Cl
I
Ag(1)–H(2)
2.21
.
3
Angle
ω
, deg
Crystals of compound
reaction solution, and their structure was solved by
I were isolated from the
B(1)H(1)Ag(1)
107
Xꢀray crystallography. Complex I represents a coordiꢀ
B(2)H(2)Ag(1)
100
91
n−
B(9)H(9)Ag(1)#2
B(10)H(10)Ag(1)#2
B(12)H(12)Ag(1)#2
nation polymer built of
[
AgB H
12
n
]
,
anionic chains
(Fig. 1a) and
1
2
which are extended along axis
с
94
+
[
Au(Ph P) ] complex cations (Fig. 1b). The atom
100
3 2
Ag(1) is coordinated by the edge B(1)–B(2) of one
Note: Atoms related to the initial atoms via symmetry transformaꢀ
2
−
tions: #1 x, –y + 3/2, z + 1/2; #2 x, –y + 3/2, z – 1/2.
B H anion and the face B(9)B(10)B(12) of the
12 12
2
−
other anion. Ag–B(H) bond lengths with B H polyꢀ
1
2
12
hedra are nonequivalent: Ag(1)–B(1) (2.498(11) Å) is
far shorter than Ag(1)–B(2) bond lengths (2.630(13) Å),
and Ag(1)–B(12) (2.528(11) Å) is shorter than Ag(1)–
tion(1) using (Bu N) B Н and Au(Ph P)Cl as the
reagents is described in [6]. Our studies have shown
4
2
6
6
3
that it is impossible to prepare a gold(I) complex of B(10) (2.614(11) Å) and Ag(1)–B(9) (2.738(11) Å).
2
−
The longest bond Ag(1)–B(9) in Fig. 1a is indicated by
a dashed line.
В Н by a similar reaction of (Bu N) B Н with
1
2
12
4
2 12 12
Au(Ph P)Cl in acetonitrile, since an isothermal evapoꢀ
3
In the complex cation [Au(Ph P) ]+, the atom
ration of the reaction mixture leads to the isolation of
3
2
Au(1) has a nearly linear coordination: angle
P(1)Au(1)P(2) is 170.91(7) ; Au(1)–P bond lengths
are 2.338(2) and 2.341(2) Å. Molecular stacking in a
crystal in the projection along axis is shown in Fig. 1c.
the least soluble compound (Au(Ph P)Cl) in colorless
3
°
crystals. Therefore, we chose [Ag B H12] and
2
12
Au(Ph P)Cl for preparing gold complexes of the closo
ꢀ
3
с
dodecaborate anion. The reaction scheme was preꢀ
sumed to be as follows:
closoꢀHydroborate anions, by virtue of their geoꢀ
metric specificity, can be coordinated to metal atoms
by various edges and/or faces of their boron cages, givꢀ
ing rise to a great many position isomers, specifically
[
Ag B Н
]
+ 2Au
(
Ph3P
)
Cl
12 12
]
P B Н + 2AgCl.
2
2
12 12
(2)
mirror isomers [18]. In compound
cocrystallize in a polymer chain: 1ꢀ2, 8ꢀ9ꢀ12 and 1ꢀ2,
ꢀ10ꢀ12 isomers (Fig. 2). Compound may be classiꢀ
fied with Cat[AgB H ] complexes where Cat =
I, two enantiomers
→
[
Au
(
Ph
)
2
3
9
I
AgCl formation was expected to remove silver from
the reaction system and to shift the reaction toward a
12 12
+
2
−
suggested gold(I) complex of the anion В Н . Howꢀ Au
(
Ph
P
)
.
As distinct from the Cat[AgB12H ] comꢀ
12
2
1
2
12
3
ever, it appeared that reaction (2) did not occur, and plexes described in [3–5] (where Cat =
+
depending on the reagent ratio, the reaction of
Ag B H ] with Au(Ph P)Cl may be described as folꢀ
+
[(NaphCH )Ph P] , NBzlEt3 ), compound
I
is the first
2
3
[
2−
12
2
12 12
3
example where the anion B H is coordinated simulꢀ
1
2
lows:
taneously by an edge to one silver(I) atom and by a
face to another silver(I) atom.
The Xꢀray crystallography and IR spectroscopic
data taken together imply that the coordination of
[
Ag B Н
]
+ Au
(
Ph3P Cl
)
2
12 12
(3)
→
[
Au
(
Ph
P
3
)
]
[
AgB12
H
]
(
I ,
)
12
2
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 4 2011

BEHAVIOR OF DODECAHYDROꢀclosoꢀDODECABORATE
а)
527
(
B(1A)
B(10A)
B(1)
B(2)
B(9)
B(2A)
B(9A)
B(12A)
Ag(1)
B(12)
(c)
B(10)
(b)
c
0
b
P(2)
P(1)
Au(1)
a
n−
+
Fig. 1. Crystal structure of compound
I: (a) a fragment of an
[
AgB H
]
chain (the anionic part), (b) [Au(Ph P) ] (the catꢀ
3 2
1
2
12
n
ionic part), and (c) projection along axis
с
(H atoms are omitted).
2
−
B H anions to Ag(I) atoms is via long and short
Complex II contains a nonanuclear gold cluster
threeꢀcenter twoꢀelectron bonds (MHB). This is eviꢀ (Fig. 3b), which constitutes the cationic part of the
denced by the values of Ag–H(B) (1.95–2.49 Å
and complex. The counterion (Fig. 3a) is the dimeric cenꢀ
Ag–B(H) (2.498(11)–2.738(11) Å) bond lengths and
AgHB bond angles (90.8 –106.8 ) (Table 2) and by the
appearance in the IR spectrum of two bands arising
1
2
12
)
3
23
−
trosymetrical trianion В Н . B–H and В···В' disꢀ
2
4
°
°
tances in the B–H–B' bridge are 1.08 and 2.154 Å,
–
1
from
1
ν
(ВН)
and having peaks at 2342 cm
(Δν
=
МВН
–1
–1
–1
2
33 cm ) and 2150 cm (Δν = 325 cm ), which refer
2
11
7
11
7
4
to longer and shorter Ag–H(B) contacts, respectively.
The study of the behavior of the closoꢀdodecaboꢀ
6
0
3
8
6
3
8
1
(12)
1
(12)
rate anion in a greater excess of Au(Ph P)Cl with
3
1
10
respect to [Аg В Н12] (where the ratio of Au(Ph P)Cl
2
12
3
to [Аg В Н12] was 9 : 1) produced a radically different
2
12
5
4
5
complex [Au (Ph P) ]В Н
(II). In this case, preꢀ
9
3
8
24 23
9
9
cisely as implied by reaction (2), AgCl is produced to
Reflection plane
1ꢀ2, 9ꢀ10ꢀ12
+
then enter a redox reaction where Ag is reduced to
2
−
1ꢀ2, 8ꢀ9ꢀ12
Ag0 and Au+ to Au0.33+ and where B H is oxidized to
1
2
12
3
−
В Н (Scheme 4). Among other reasons, the formaꢀ
2
4
23
2
−
Fig. 2. Schematics of enantiomers 1ꢀ2, 8ꢀ9ꢀ12 and 1ꢀ2, 9ꢀ
tion of degradation products of B H is responsible
1
2
12
10ꢀ12 that cocrystallize in the crystal of complex
view).
I (top
for the low yield of compound II
.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 4 2011

528
AVDEEVA et al.
complex [Au (Ph P) ](NO ) [23]. Other reducing
(а)
9
3
8
3 3
3+
agents are also useful for preparing [Au (Ph P) ] , for
9
3
8
example, the titanium complex [Ti(
η
ꢀC H Me)2] [24].
5 5
In our case, the reducing agent is likely to be the initial
2
−
closoꢀdodecaborate anion B H .
1
2
12
To summarize, we may say that having studied the
2
−
behavior of the closoꢀdodecaborate anion B H in
1
2
12
reaction with Au(Ph P)Cl, we found a number of feaꢀ
3
tures of the complexing process. We have found that
+
+
Cat B H salts of organic cations (Cat = Ph P ,
2
12 12
4
Bu N+) do not react with Au(Ph P)Cl in acetonitrile,
(b)
4
3
whereas the use of [Ag B H12] as the precursor closo
ꢀ
2
12
dodecaborate and variation of the reagent ratio proꢀ
duce fundamentally different products. The equimolar
ratio of [Ag B H12] to Au(Ph P)Cl yields a silver(I)
Au(5)
2
12
3
Au(2)
complex that is the first example where the closo
ꢀ
Au(3)
Au(4)
Au(4A)
Au(3A)
dodecaborate anion is coordinated to silver(I) atoms
Au(1)
in the face coordination. The reaction of [Ag B H12]
2
12
with an excess of Au(Ph P)Cl generates ideal condiꢀ
3
Au(5A)
3–
3+
tions for preparing [В Н ] and [Au (Ph P) ]
,
24
23
9
3
8
Au(2A)
whereas the preparation of the aforementioned cation
and anion individually requires applying more severe
conditions. Both complexes contain gold atoms,
which are however not linked to the cluster boron
anion.
Fig. 3. Crystal structure of compound II: (a) [В24Н23]3–
3+
(
anionic part) and (b) [Au (Ph P) ] (cationic part).
9 3 8
ACKNOWLEDGMENTS
respectively in match with theoretical calculations
The authors are grateful to Xꢀray Structure
Research Center of the Institute of Organoelement
Compounds, Russian Academy of Sciences, for carryꢀ
ing out the diffraction experiment on a crystal of comꢀ
plex II. This work was supported by the Program for
Support of Leading Scientific Schools (grant
no. NShꢀ1518.2008.3) and the Russian Foundation
for Basic Research (project no. 07ꢀ03ꢀ00637).
3
−
[
19]. The existence of the trianion В Н in complex
24 23
11
II is unambiguously identified by B NMR and IR
spectroscopy [9].
3
+
Compounds of the cation [Au (Ph P) ] and anion
9
3
8
3–
[
В Н ] with other counterions are known in the litꢀ
24 23
2
−
erature. The oxidation of B H to yield trianion
В Н ] was described as early as in 1969 [20];
1
2
12
3–
[
24 23
Na [В Н ] was obtained by electrolysis of a solution
3
24 23
REFERENCES
of Na B H in acetonitrile at 1.5 V:
2
12 12
1
.
The Chemistry of Inorganic Hydrides. Collected Works
Ed. by N. T. Kuznetsov (Nauka, Moscow, 1990) [in
Russian].
,
2
12
−
3−
+
2
B H
В Н + Н + 2e.
24 23
1
2
Based on the data of elemental analysis and IR and
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