Facile one-pot synthesis of triphenylbismuth(V) bis(carboxylate) complexes

Article abstract of DOI:10.1021/om500337z

Triphenylbismuth(V) bis(carboxylates), Ph₃Bi(O ₂CR)₂ (R = 5-Br-2-OH-C₆H₃ (1), 2-OH-C₆H₄ (2), 2,6-(OH)₂-C₆H ₃ (3), 3-Me-2-NH₂-C₆H₃ (4), Ph (5), Me (6)), were obtained from the reaction of triphenylbismuth with hydrogen peroxide and excess carboxylic acid in wet 2-propanol. The synthesis avoids the use of halogens as oxidants, and the products crystallize directly from the solution as pure compounds. They crystallize from solution without further need for purification. The structures of 1-5 were confirmed by single-crystal X-ray diffraction. Compounds 2 and 5 exhibit a polymorph different from that previously reported in the literature. While all of the Bi(V) compounds adopt a trans-axial trigonal-bipyramidal configuration with the carboxylates in axial positions, there is considerable variation in the coordination of the carboxylate that ranges from simple η¹ to a mixture of mono- and bidentate chelating bonding modes.

Full text of DOI:10.1021/om500337z

Note
pubs.acs.org/Organometallics
Facile One-Pot Synthesis of Triphenylbismuth(V) Bis(carboxylate)
Complexes
Ish Kumar,† Prateek Bhattacharya,† and Kenton H. Whitmire*
Department of Chemistry, MS60, Rice University, 6100 Main Street, Houston, Texas 77005-1892, United States
S
* Supporting Information
ABSTRACT: Triphenylbismuth(V) bis(carboxylates), Ph3Bi-
(O2CR)2 (R = 5-Br-2-OH-C6H3 (1), 2-OH-C6H4 (2), 2,6-
(OH)2-C6H3 (3), 3-Me-2-NH2-C6H3 (4), Ph (5), Me (6)),
were obtained from the reaction of triphenylbismuth with
hydrogen peroxide and excess carboxylic acid in wet 2-propanol.
The synthesis avoids the use of halogens as oxidants, and the
products crystallize directly from the solution as pure
compounds. They crystallize from solution without further
need for purification. The structures of 1−5 were confirmed by
single-crystal X-ray diffraction. Compounds 2 and 5 exhibit a
polymorph different from that previously reported in the
literature. While all of the Bi(V) compounds adopt a trans-axial
trigonal-bipyramidal configuration with the carboxylates in axial
positions, there is considerable variation in the coordination of
the carboxylate that ranges from simple η1 to a mixture of mono- and bidentate chelating bonding modes.
rganobismuth compounds, particularly bismuth carbox-
ylates, have antimicrobial properties and are commonly
or to detect it spectroscopically in solution were not successful.
In the absence of the carboxylic acid we observed
decomposition and side products rather than the formation
of a stable complex.
Further study of this reaction proved it to be general and
applicable to a diverse set of carboxylic acids, as illustrated in
Figure 1. Salicylic acid and its derivatives were targeted because
(i) they display wide variety of chemotherapeutic properties
such as antibacterial and antiparasitic activity27,28 and (ii) they
possess a wide variety of coordination modes29,30 which can be
useful in the construction of organic frameworks. Our group
has previously reported the structure of Bi(Hsal)3 adducts with
nitrogen-containing chelating ligands and monophenylbismuth
O
used as pharmaceutical agents in chemotherapy and in the
treatment of Helicobacter pylori infections.1 The versatility of
these bismuth compounds in organometallic reactions also
enables them to be extensively used in the synthesis of
heterobimetallic complexes2 and as catalysts.3,4 Triphenylbis-
muth undergoes reactions with 3 equiv of carboxylic acids in
the presence of polar and nonpolar solvents to yield complete
replacement of the aryl groups, but these compounds are often
sensitive to hydrolysis and oxo-cluster compounds result.5−7
Nuclearities up to 38 bismuth atoms have been reported.5,8,9 It
is possible to obtain monophenyl bismuth(III) dicarboxylato
compounds by careful addition of stoichiometric amounts of
the carboxylic acid.10,11 Interestingly, conducting these
reactions in reagent-grade 2-propanol led to isolation of
triphenylbismuth(V) bis(carboxylates), whose formation we
were ultimately able to trace to the presence of peroxides in the
solvent, which was confirmed by qualitative analysis. Normally,
these compounds are prepared in a two-step process, first by
reacting BiPh3 with chlorine or bromine to produce Ph3BiX2
followed by reaction with an alkali-metal salt of an appropriate
anionic ligand.12 Several examples of BiPh3(O2CR)2 have been
reported previously (R = Me,13,14 Et,14 Ph,13,14 Bu,13
CHCH2,13 Me(CH2)8,13 Me(CH2)10,13 oxalate,13 p-
OHC6H4CH2CH2,15 Cl3C,16 ClCH2,16 BrCH2,16 F3C,17 3-
MeC6H4,18 4-MeC6H4,18 2-AcOC6H4,18 F5C6,19 3,4,5-F
C6H2,20 C3H521). Bi(V) compounds have been studied
extensively as aryl transfer reagents in organic synthesis.22−26
We have presumed that the reaction proceeds through the
intermediacy of Ph3BiO, but attempts to isolate that compound
Figure 1. Acids used in the present study: (A) 5-bromosalicylic acid;
(B) salicylic acid; (C) 2,6-dihydroxybenzoic acid; (D) 3-methylan-
thranilic acid; (E) benzoic acid; (F) acetic acid.
Received: March 28, 2014
© XXXX American Chemical Society
A
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Organometallics
Note
carboxylate complexes, [PhBi(O2CR)] (where R = 2-OH-
C6H4, 4-Me-2-OH-C6H3).7,10 Recently we also reported the
structure of the simplest oxo cluster, [Bi4(μ3-O)2(Hsal)8],
containing a salicylate ligand.9 The yield and physical properties
of all complexes prepared are provided in the Supporting
Information. A detailed comparison of the bismuth(V)
carboxylato complexes is presented here and shows systematic
variation in the structural parameters of the compounds as a
function of the carboxylate used.
The complexes are stable in the solid state and are soluble in
acetone and DMSO. All of the complexes were characterized by
NMR spectroscopy, IR spectroscopy, elemental analyses, and
melting points. Molecular structures were confirmed using
single-crystal X-ray diffraction. The structures of 231 and 520
have been previously determined, although those reported here
are new polymorphs. Pictures of the new compounds 1 and 4
are presented in Figures 2 and 3, respectively. Figures of the
other molecules are given in the Supporting Information. The
selected Bi−O(carboxylate), O−Bi−O, and Bi−O−C angles of
1−5 are reported in Table 1.
Complexes 1−5 have distorted-trigonal-bipyramidal geome-
try with the carboxylate oxygen atoms in the axial positions and
the carbon atoms of the phenyl groups in equatorial positions.
One of the phenyl groups in 3 is disordered over two positions,
and three carbons of another aryl group are slightly disordered;
this could not be resolved. Both carboxylate ligands in 1−3
bind in an η1(O) fashion, whereas for 4 both bind in a
symmetrical η2(O,O′) fashion. In 5, there are two molecules in
the asymmetric unit; in one of the molecules both carboxylate
ligands bind in a η1(O) fashion, whereas for the other molecule
the carboxylate ligands bind in both η2(O,O′) and η1(O)
modes. The bonding modes of the oxygen atom of the
carboxylate ligands vary from monodentate to a mixture of both
monodentate and bidentate modes (Figure 4). The IR spectra
Figure 4. Variation in the bonding modes of the carboxylate oxygen.
of all the complexes show asymmetrical and symmetrical
stretching carboxylate modes. Complexes 1−3 display a Δν
value (Δν = νasymm − νsymm) greater than 200 cm−1, indicating a
monodentate bonding mode as observed in the solid-state
structure, whereas complexes 4 and 5 exhibit Δν values less
than 200 cm−1, consistent with the bidentate bonding mode
observed in their solid-state structures.
Figure 2. Molecular structure of 1. Phenyl hydrogens have been
omitted for clarity.
The Bi−O(carboxylate) bond lengths and O−Bi−O and Bi−
O−C bond angles of complexes 1−5 are consistent with the
corresponding distances and angles of other triphenylbismuth-
(V) bis(carboxylate) complexes reported in the literature.15−17
The structural data show a correlation between the pKa values
of the carboxylate ligands and Bi−O bond lengths, with the
weaker acids having shorter Bi−O distances. Interestingly, the
average Bi−O distance is the same for both independent
molecules in spite of the variation in Bi−carboxylate binding.
The Bi−O−C bond angles, where the O atom is that in the
axial position which always has the shorter Bi−O distance, were
also considered, as this value should correlate with a tilt of the
carboxylate group; a smaller angle corresponds to a greater tilt.
The less acidic carboxylates exhibit a greater angle (see the
Supporting Information Table S2), which corresponds to an
Figure 3. Molecular structure of [BiPh3(3-CH3-2-NH2-C6H3CO2)2]
(4). Phenyl hydrogens have been omitted for clarity.
Table 1. Selected Bond Lengths (Å) and Angles (deg) for 1−5
1 (X = 1)
2 (X = 1)
3 (X = 1)
4 (X = 1)
5 (X = 1)
5 (X = 2)
Bi(X)−O(X11)
Bi(X)−O(X12)
Bi(X)−O(X21)
Bi(X)−O(X22)
O(X11)−Bi(1)−O(X21)
Bi(X)−O(X11)−C(X17)
Bi(X)−O(X21)−C(X27)
2.292(3)
3.016(4)
2.278(3)
2.997(3)
172.6(1)
112.0(3)
111.4(3)
2.290(3)
2.859(3)
2.247(3)
2.869(3)
170.6(1)
108.2(3)
109.2(3)
2.291(3)
2.916(3)
2.329(3)
2.862(3)
170.7(1)
110.2(2)
107.1(3)
2.263(6)
2.755(7)
2.283(6)
2.699(7)
170.7(2)
105.9(5)
103.5(5)
2.254(4)
2.886(5)
2.270(4)
2.795(4)
170.3(1)
108.9(3)
104.9(3)
2.290(4)
2.752(4)
2.272(4)
2.893(4)
172.2(1)
103.9(3)
107.7(3)
B
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Organometallics
Note
were referenced to tetramethylsilane (TMS). Melting points were
obtained in sealed capillaries on an Electrothermal melting point
instrument. Elemental analyses (C, H, N) were performed at Galbraith
Laboratories. IR spectra were recorded on a Perkin-Elmer FTIR
spectrometer.
increased interaction between the Bi and the second oxygen
atom of the carboxylate ligand. Figures S6 and S7 have been
provided in the Supporting Information in support of the above
statement. A high correlation (R2 = 0.91) exists between the
average Bi−O bond lengths and their corresponding Bi−O−C
angles (Figure S8 in the Supporting Information). This is a
logical consequence of higher charge localization on the
carboxyl group with increasing pKa orienting both oxygen
atoms of the carboxyl group toward the metal center. In
complexes 1−3 the OH groups are intramolecularly H-bonded
to an oxygen atom of the carboxylate, and these secondary
interactions can explain the larger deviations of 1 and 3 in the
plot. In the case of the bromo derivative 1, the acidity of the
OH group would be enhanced, allowing it to more strongly
internally hydrogen bond to the carboxylate ligand, while the
presence of the second OH group in 3 would tend to offset the
tilting effect.
General Synthetic Procedure. BiPh3 (0.33 mmol) and the
appropriate carboxylic acid (1.00 mmol) were combined and dissolved
in 8.0 mL of reagent grade 2-propanol (used as received from Fisher
Scientific) by stirring on low heat for 2 min. The homogeneous
solutions were stored at room temperature for 2−3 days while crystals
formed. The crystals were isolated, dried, and identified as Bi(V)
complexes. The composition of these complexes is given in Table 1.
The analytical data have been provided in the Supporting Information.
The experiment was repeated by performing the reaction in distilled 2-
propanol with the addition of 30% H2O2 solution (5 μL). The results
obtained were the same, but the yield obtained through this synthetic
method was generally higher than that in the absence of added
peroxide. There was a trace amount of 2-propanol (<1%) present in
the NMR spectrum for some of the Bi(V) complexes.
The distances between the nonbonded oxygen atoms and the
bismuth atom (i.e., Bi---O(C)) in 1−3 and 5 are as follows:
3.016(4) and 2.997(3) Å, 1; 2.869(3) and 2.859(3) Å, 2;
2.916(3) and 2.863(3) Å, 3; 2.893(5), 2.856(5), and 2.795(4)
Å, 5. These indicate substantially weaker interactions between
the second oxygen atoms and the metal center. Comparison of
the Bi- - -O(C) distances in 1−5 indicates that the degree of
bidentate coordination is slightly greater in 4 than in the others,
whereas it is a minimum in 1. This may be due to the presence
of an electron-withdrawing group in 1. The Bi- - -O(C)
distance in 1 is similar to that reported for BiPh3(CF3CO2)2
(2.980 Å).17 The O−Bi−O angle is expected to be 180° for an
idealized trigonal bipyramid, but these compounds show
significant deviation from linearity with values ranging from
170.3 to 172.6° (Supporting Information, Table S2). This
distortion exhibits itself further in the C−Bi−C angles, which
show a bimodal range: 106.5(2)−139.8(2)° (1), 106.9(2)−
140.3(2)° (2), 105.1(2)−141.4(2)° (3), 102.9(3)−148.8(3)°
(4), and 105.8(2)−144.4(2)° (for Bi1) and 103.9(2)−
148.3(2)° (for Bi2) (5). One angle is substantially larger than
the other two to accommodate the demands of the weaker
binding to the second carboxylate oxygen atoms. Nevertheless,
the sum of C−Bi−C angles (i.e., C−Bi−C) still indicates a
planar arrangement of these groups (deg): 359.8 (1), 359.7 (2),
360.0 (3), 360.0 (4), 360.0 and 359.7 (5).
Analytical Data for Complexes 1−6. [BiPh3(5-Br-2-OH-
C6H3CO2)2] (1). Anal. Found for C32H25BiBr2O6: C, 43.43; H, 2.76.
1
Calcd: C, 43.96; H, 2.88. H NMR (500 MHz, d6-acetone, 30 °C): δ
8.36 (d of d, 6H, J = 8.5 Hz, o-PhH), 7.92 (s, 2H, ArH), 7.82 (m, 6H,
m-PhH), 7.65 (m, 3H, p-PhH), 7.51(d, 2H, J = 9 Hz, Ar-H), 6.79 (d,
2H, J = 9 Hz, Ar-H). 13C NMR (125 MHz, d6-acetone, 30 °C): δ 161.4
(CO), 159.4 (C-OH), 138.3 (Ar-C), 135.1 (Ph-C), 133.0 (Ph-C),
132.8 (Ph-C), 131.3 (Ar-C), 120.0 (Ar-C), 117.5 (C-COO), 110.5 (C-
Br). IR (ν, cm−1): 3211 (br), 1643 (m), 1576 (m), 1483 (m), 1442
(m), 1403 (m), 1363 (m), 1292 (m), 1267 (m), 1220 (s), 1129 (m),
1033 (m), 820 (s), 698 (s), 627 (m), 573 (m).
[BiPh3(2-OH-C6H4CO2)2] (2). Anal. Found for C32H25BiO6: C,
1
53.67; H, 3.69. Calcd: C, 53.78; H, 3.50. H NMR (500 MHz, d6-
DMSO, 30 °C): δ 8.36 (d of d, 6H, J = 8.4 Hz, o-PhH), 7.85 (d of d,
6H, J = 8.1 Hz, ArH), 7.79 (m, 6H, m-PhH), 7.62 (m, 3H, p-PhH),
7.37(m, 2H, ArH), 6.80 (m, 2H, ArH). 13C NMR (125 MHz, d6-
acetone, 30 °C): δ 162.3 (CO), 159.9 (C-OH), 135.7 (Ar-C), 135.0
(Ph-C), 132.8 (Ph-C), 132.6 (Ph-C), 132.0 (Ar-C), 119.4 (Ar-C),
117.6 (Ar-C), 115.7 (Ar-C). IR (ν, cm−1): 3060 (br), 1740 (m), 1625
(m), 1688 (m), 1481 (s), 1445 (w), 1375 (s), 1308 (w), 1247 (m),
1217 (m), 1158 (w), 1091 (w), 1032 (w), 866 (m), 815 (m), 757 (s),
701 (s), 666 (s).
[BiPh3{2,6-(OH)2-C6H3CO2}2] (3). Anal. Found for C32H25O8Bi: C,
1
50.89; H, 3.35. Calcd: C, 51.34; H, 3.64. H NMR (500 MHz, d6-
acetone, 30 °C): δ 8.13 (d, 6H, J = 7.6 Hz, o-PhH), 7.85 (m, 6H, m-
PhH), 7.68 (m, 3H, p-PhH), 7.06 (t, J = 8 Hz, 2H, ArH), 6.15 (d, J =
8.1 Hz 4H, ArH). 13C NMR (125 MHz, d6-acetone, 30 °C): δ 162.5
(CO), 159.5 (C-OH), 138.4 (Ar-C), 135.1 (Ph-C), 133.4 (Ar-C),
133.2 (Ar-C), 131.3 (Ph-C), 128.6 (Ar-C), 107.6 (C-COO). IR (ν,
cm−1): 3224 (br), 1638 (s), 1579 (m), 1442 (m), 1360 (m), 1269 (s),
1219 (s), 1154 (m), 1126 (m), 1032 (s), 852 (m), 818 (m), 768 (w),
674 (m), 648 (w), 605 (m).
[BiPh3(3-CH3-2-NH2-C6H3CO2)2] (4). Anal. Found for
C34H33BiN2O4: C, 55.24; H, 4.28; N, 3.89. Calcd: C, 54.99; H, 4.48;
N, 3.77. 1H NMR (500 MHz, d6-acetone, 30 °C): δ 8.34 (d of d, J = 7
Hz, 6H, o-PhH), 7.75 (d of d, 2H, J = 7.1 Hz, m-PhH), 7.68 (t, 6H, m-
PhH), 7.54 (m, 3H, p-PhH), 7.06 (d, J = 7.2 Hz, 2H, Ar-H), 6.42 (t, J
= 7.5 Hz, 2H, ArH), 6.27 (s(br), 4H, NH2), 2.08 (s, 6H, CH3). 13C
NMR (125 MHz, d6-acetone, 30 °C): δ 160.3 (CO), 150.2 (C-
NH2), 134.8 (Ar-C), 134.7 (Ph-C), 132.2 (Ph-C), 131.7 (Ph-C), 131.3
(Ar−C), 123.6 (Ar-C), 115.4 (Ar-C), 113.4 (Ar-C), 17.7 (Ar-CH3). IR
(ν, cm−1): 3488 (w), 3346 (m), 1605 (m), 1532 (s), 1468 (s),
1434(s). 1374 (m), 1350 (m), 1319 (s), 1285 (m), 1252 (s), 1083 (s),
983 (s), 780 (s), 728(vs), 677 (s), 632 (s).
Examination of the structure of 5 for possible void areas
using Platon (version 161012)32 was consistent with the
presence of water, as also indicated by the analytical and
spectroscopic data. The total potential solvent area volume was
found to be 69.5 Å3.
CONCLUSIONS
■
A facile and general one-pot synthesis of bismuth(V)
bis(carboxylate) complexes was developed that gives good
yields of pure, crystalline products without the use of chlorine
or bromine. The average Bi−O bond lengths tend to be shorter
and the Bi−O−C angles smaller for the less acidic RCO2H
acids, indicating that these ligands are more strongly bound and
tend to have both oxygen atoms of the carboxylate ligand
interacting with the metal center.
[BiPh3(PhCO2)2]·H2O (5). Anal. Found for C32H27BiO4: C, 54.05; H,
3.70. Calcd: C, 54.8; H, 3.85. 1H NMR (500 MHz, d6-acetone, 30 °C):
δ 8.37 (m, 6H, o-PhH), 7.96 (m, 2H, Ar-H), 7.70 (m, 6H, m-PhH),
7.55 (m, 3H, p-PhH), 7.49 (m, 2H, Ar-H), 7.37 (m, 2H, Ar-H), 6.83
(s, 1H, OH). 13C NMR (125 MHz, d6-acetone, 30 °C): δ 161.4 (C
O), 134.1 (Ph-C), 133.3 (Ar-C), 132.0 (Ar-C), 131.5 (Ph-C), 131.2
(Ar-C), 130.0 (Ar-C), 128.2 (Ph-C). IR (ν, cm−1): 3430 (br), 1603
EXPERIMENTAL SECTION
■
Materials and Equipment. All reagents and chemicals, unless
otherwise stated, were purchased from commercial sources. NMR
spectra were recorded at room temperature in d6-acetone on a
BrukerAvance 500 spectrometer, and the H and 13C chemical shifts
1
C
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Organometallics
Note
(m), 1564 (m), 1489 (m), 1446 (m), 1397 (m), 1339 (s), 1298 (m),
1261 (m), 1226 (m), 1171 (w), 1132 (w), 1068 (m), 1022 (m), 847
(m), 803 (w), 741 (m), 717 (s), 681 (s). The IR band at 3430 cm−1 is
consistent with the presence of water in the sample, although the water
molecule could not be located in the X-ray structure.
(8) Mansfeld, D.; Miersch, L.; Ruffer, T.; Schaarschmidt, D.; Lang,
̈
H.; Bohle, T.; Troff, R. W.; Schalley, C. A.; Muller, J.; Mehring, M.
̈
̈
Chem. Eur. J. 2011, 17, 14805.
(9) Boyd, T. D.; Kumar, I.; Wagner, E. E.; Whitmire, K. H. Chem.
Commun. 2014, 50, 3556.
[BiPh3(MeCO2)2] (6). Anal. Found for C32H25BiBr2O6: C, 46.65; H,
3.72. Calcd: C, 47.15; H, 4.14. H NMR (500 MHz, d6-acetone, 30
(10) Stavila, V.; Fettinger, J. C.; Whitmire, K. H. Organometallics
2007, 26, 3321.
1
°C): δ 8.15 (d of d, J = 8.4 Hz, 6H, o-PhH), 7.67 (m, 6H, m-PhH),
7.56 (m, 3H, p-PhH), 1.72 (s, 6H, CH3). 13C NMR (125 MHz, d6-
acetone, 30 °C): δ 134.7 (Ph-C), 131.9 (Ph-C), 131.7 (Ph-C). IR (ν,
cm−1): 1586 (m), 1559 (m), 1470 (s), 1438 (m), 1383 (s), 1327 (s),
1251 (m), 1166 (w), 1086 (w), 1053 (m), 1011 (m), 984 (s), 935 (w),
780 (w), 746 (m), 728 (s), 678 (m), 666 (s), 622 (m).
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X-ray Structural Determinations. Single crystals of 1−5 suitable
for X-ray crystallography were separated as thin needles directly from
the aforementioned reactions. Intensities were measured at 173 K on
Rigaku SCX Mini diffractometer using a CCD area detector with Mo
Kα radiation (λ = 0.71073 Å). Empirical absorption correction using
the program SADABS was applied to the data. The structures were
solved using direct methods and refined against F2 with the SHELXTL
software package.33 All non-hydrogen atoms in the complexes were
refined anisotropically. Hydrogen atoms were idealized throughout the
convergence process. Figures presented in this publication were
created with the programs in the Diamond (version 3.2i) software
package.34
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ASSOCIATED CONTENT
■
S
* Supporting Information
Tables, figures, and CIF files giving yields, melting points, and
color of Ph3Bi(O2CR)2, pKa values, Bi−O bond lengths (Å)
and Bi−O−C bond angles (deg), crystallographic data for 1−5,
all bond lengths and angles, fully labeled anisotropic displace-
ment ellipsoid diagrams of all compounds, and correlations
between pKa and Bi−O bond lengths/Bi−O−C bond angles.
This material is available free of charge via the Internet at
http://pubs.acs.org.
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AUTHOR INFORMATION
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(27) Wu, K. K. Anti-Inflammatory Anti-Allergy Agents Med. Chem.
2007, 6, 278.
(28) Thomas, M. R. In Kirk-Othmer Encyclopedia of Chemical
Technology; Wiley: Hoboken, NJ, 2006.
Corresponding Author
*K.H.W.: e-mail, whitmir@rice.edu; fax, 713-348-5652; tel:
713-348-5650.
(29) Yin, M.-C.; Ai, C.-C.; Yuan, L.-J. J. Mol. Struct. (THEOCHEM)
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(30) Song, J.-F.; Chen, Y.; Li, Z.-G.; Zhou, R.-S.; Xu, X.-Y.; Xu, J.-Q.;
Author Contributions
†These authors contributed equally.
Notes
Wang, T.-G. Polyhedron 2007, 26, 4397.
The authors declare no competing financial interest.
(31) Feham, K.; Benkadari, A.; Chouaih, A.; Miloudi, A.; Boyer, G.;
El-Abed, D. Cryst. Struct. Theory Appl. 2013, 2, 28.
(32) Spek, A. L. Acta Crystallogr., Sect. D 2009, D65, 148.
ACKNOWLEDGMENTS
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(33) Sheldrick, G. M. SADABS 5.1; University of Gottingen,
̈
The Robert A. Welch Foundation (C-0976) is gratefully
acknowledged for support of this work.
Gottingen, Germany, 1997.
̈
(34) Brandenburg, K. Diamond 3.2i; Crystal Impact, Bonn, Germany,
1997−2012.
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dx.doi.org/10.1021/om500337z | Organometallics XXXX, XXX, XXX−XXX