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Concept Paper

Gold(III) Complexation in the Presence of the Macropolyhedral Hydridoborate Cluster [B20H18]2−

by
Varvara V. Avdeeva
1,*,
Anna V. Vologzhanina
2,
Alexey S. Kubasov
1,
Nailya S. Akhmadullina
3,
Oleg N. Shishilov
4,
Elena A. Malinina
1 and
Nikolay T. Kuznetsov
1
1
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, 119991 Moscow, Russia
2
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova Str. 28, 119991 Moscow, Russia
3
Baikov Institute of Metallurgy and Material Science, Russian Academy of Sciences, Leninskii pr. 49, 119334 Moscow, Russia
4
Physical Chemistry Department, Lomonosov Institute of Fine Chemical Technologies, MIREA—Russian Technological University, pr. Vernadskogo 86, 119571 Moscow, Russia
*
Author to whom correspondence should be addressed.
Inorganics 2022, 10(7), 99; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070099
Submission received: 22 June 2022 / Revised: 7 July 2022 / Accepted: 8 July 2022 / Published: 10 July 2022
(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)
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Versions Notes

Abstract

:
Gold(III) complexation with the octadecahydrido-eicosaborate anion [B20H18]2− was studied for the first time. It was found that when gold(III) complexes [Au(L)Cl2]BF4 (L = bipy, phen) reacted with [B20H18]2−, complexes [Au(L)Cl2]2[B20H18] were isolated. The compounds consisted of a cationic gold(III) complex [Au(L)Cl2]+ and the hydridoborate cluster as a counterion. X-ray diffraction studies revealed weak B–H...Au interactions for both compounds. Note that more reactive anions [BnHn]2− (n = 10, 12) in similar reactions with gold(III) complexes resulted in gold mirror reactions.

Graphical Abstract

1. Introduction

Higher polyhedral boron dianions [BnHn]2− (n = 6–12) [1,2,3,4,5] (n.b., hydridoborate is the new IUPAC recommended name for this class of compounds [6]) are fascinating ligands in coordination chemistry of transition metals. On the one hand, due to their 3D aromaticity [7,8,9,10,11] and low charge density, they are typical soft Lewis bases, which form numerous stable complexes with the soft metal acids including copper(I) and silver(I) [12,13,14,15], zinc(II) and cadmium(II) [16,17,18,19], and lead(II) ([20] and references therein). In addition, the boron cluster anions form compounds with metal(II) complex cations acting as counterions, e.g., Cu(II), Fe(II), Co(II), Ni(II), and Mn(II) [15,21,22,23,24,25,26]. In the presence of metals(III) complexes, the boron cluster anions act as reducing agents being oxidized to oxidoborates [27,28,29]. On the other hand, boron clusters form numerous products of the substitution of terminal hydrogen atoms by various functional groups keeping the initial closo-structure [30,31,32,33,34].
The closo-decaborate anion [B10H10]2− can be easily oxidized in the presence of Fe(III) or Ce(IV) salts to form a macropolyhedral boron cluster [trans-B20H18]2− [35,36], and the coordination chemistry of the latter began to be studied only a few years ago. A number of silver(I) compounds with the coordinated macropolyhedron and Ph3P ligand were isolated and characterized by X-ray diffraction; the single-crystal-to-single-crystal transformations initiated with UV radiation and high temperature were studied [37,38]. First lead(II) complexes with coordinated Bipy and [B20H18]2− were synthesized and characterized by IR spectroscopy and X-ray diffraction [38]. Tris-chelate manganese complex [Mn(Bipy)3][B20H18] [39] and iron(II) complex [CpFe(Cp-CH2-NMe2Et2)][B20H18] [40] with the boron clusters in the outer sphere are also known.
A number of gold compounds with boron clusters were synthesized and characterized. In particular, the gold(I) complex with triphenylphosphine and the hexahydrido-closo-hexaborate anion {Au2(Ph3P)4[B6H6]} was reported [41]. The compound is a binuclear complex containing a closo-hexaborate anion as a bridging ligand coordinated to the gold(I) atoms via opposite B3 faces. The complex with a direct metal–boron bond {Au3(Ph3P)3[B10H9]} [42] was obtained by the reaction of [Au(Ph3P)Cl] with {Ag2[B10H10]} in the acetonitrile/benzene system. A triangular Au3 fragment can be considered as a substituent in the apical position of the boron cluster.
Gold(I) compounds with an outer-sphere coordination of the boron clusters were also described. Complexes [Au(Ph3P)x]2[B12Hal12] (Hal = F, Cl, Br, I; x = 2, 3) with perhalogenated boron clusters in the outer sphere were isolated [43] from the electrochemically assisted reactions of (H3O)2[B12Hal12] acids with Au0 in the presence of Ph3P. Structures of mononuclear gold(I) complexes [(CH3CN)2Au][B12Cl11(Me3N)]·CH2Cl2 and [(Ph3P)2Au2Cl][B12Cl11(Me3N)] [44], as well as binuclear gold(I) complex [Ph3PAuClAuPh3P][B12Cl11(Me3N)] [45] with a substituted closo-dodecaborate anion [B12Cl11(Me3N)]−, were also reported. In addition, polymeric chain complex [Au(Ph3P)2][Ag[B12H12]]n was isolated [46].
It is noteworthy that the reaction of [Au(Ph3P)Cl] with {Ag2[B12H12]} gave a gold complex [Au9(PPh3)8][B24H23] [42]. The nine-vertex gold cluster [Au9(PPh3)8]3+ is a cationic part of the compound, while the [B24H23]3− trianion with a linear B–H–B′ bridge is a counterion and shows a centrosymmetric structure.
Complexes of metals in a high oxidation state are extremely rare. Usually, metals(III) are reduced to metals(II) because of reducing properties of boron clusters. As far as we know, a few examples of iron(III) and cobalt(III) complexes have been reported. Binuclear iron(III) complex [{(η5–Cp)(dppe)Fe}2{µ2–1,10-NC[B10H8]CN)}]·H2O was isolated with disubstituted 1,10-derivative [B10H8(CN)2]2−, which acts as a bridge ligand between two metal complexes with cyclopentadienyl and phosphine ligands [47]. In addition, the cobalt(III) complex with the least reactive closo-dodecaborate anion [CoIII(Phen)3][B12H12]NO3∙2DMF∙4H2O was isolated [48].
Here, we describe the results of our study of gold(III) complexation in the presence of a [B20H18]2− anion. First, gold(III) complexes with boron cluster anions were isolated and characterized.

2. Experimental

2.1. Synthesis

All reactions were carried out in air. Acetonitrile (HPLC grade), ethanol (95%), bipy (98%), and Ph3P (98%) were purchased from Sigma-Aldrich. (Et3NH)2[B10H10] was synthesized from decaborane(14) according to the known procedure [49]. (Et3NH)2[trans-B20H18] was prepared by oxidation of aqueous (Et3NH)2[B10H10] with FeCl3 according to the procedure reported [35,50]. The obtained solid was dissolved in a CH3CN/water mixture followed by the addition of aqueous Ph4PCl in the reaction solution resulting in the quantitative precipitation of (Ph4P)2[B20H18]. [Au(bipy)Cl2]BF4 and [Au(phen)Cl2]BF4 were prepared according to the known procedure [51].
Synthesis of [Au(L)Cl2]2[B20H18] (1: L = bipy, 2: L = phen)
A solution of [Au(L)Cl2]BF4 (0.2 mmol) in acetonitrile was added with stirring to a solution of (Ph4P)2[B20H18] (0.1 mmol) in acetonitrile (10 mL). The formation of dark-orange crystals was observed within 5–10 min. The crystals were filtered off and dried in air. The yield was ~90%. Single crystals 1·2CH3CN and 2·2CH3CN suitable for X-ray diffraction study were taken from the reaction solutions.
Anal. calcd. for Au2C20H34N4Cl4B20 (1): C, 22.2; H 3.2; N, 5.2; B 20.0. Found, %: C 22.3; H 3.1; N, 5.1; B 19.9. IR (NaCl, ν, cm−1): ν(BH) 2540, 2515, 2501, 2470; ν(CN)CH3CN 2355, 2335;δ(BBH) 1029; 1605w, 1507w, 1456, 1377, 1320, 1249w, 1113w, 1077w, 1047w; 771. NMR 11B (dmso-d6, ppm): −30.7 (d, 2Bap), −16.2 (s, 2B, B2, B2′), −6.0 (d, 2Beq), −11.7 (d, 4Beq), −15.3 (d, 4Beq), −18.8 (d, 4Beq), −25.1 (d, 2Bap).
Anal. calcd. for Au2C24H34N4Cl4B20 (2): Au, 34.8; C, 25.5; H 3.0; N, 5.0; B 19.1. Found, %: Au, 34.3; C 24.8; H 2.9; N, 5.0; B 19.0. IR (NaCl, ν, cm−1): ν(BH) 2530, 2490; ν(CN)CH3CN 2360, 2332; δ(BBH) 1030; 1602w, 1518w, 1461s, 1432, 1377, 1221w, 1153w, 954w, 871w; 847, 823w, 748w, 723w, 701w, 673w. NMR 11B (dmso-d6, ppm): −31.0 (d, 2Bap), −16.9 (s, 2B, B2, B2′), −5.9 (d, 2Beq), −11.6 (d, 4Beq), −15.2 (d, 4Beq), −18.7 (d, 4Beq), −24.9 (d, 2Bap).

2.2. Materials and Methods

Elemental analysis for carbon, hydrogen, and nitrogen was performed using a Carlo ErbaCHNS-3 FA 1108 automated elemental analyzer. Boron and metal contents were determined on an iCAP 6300 Duo ICP emission spectrometer with inductively coupled plasma. Samples were dried in air to constant mass; thus, solvent-free samples 1 and 2 were used.
IR spectra of compounds were recorded with a Lumex Infralum FT-02 FTIR-spectrometer in the range of 4000–600 cm−1 at a resolution of 1 cm−1. Samples were prepared as Nujol mulls; NaCl plates were used. Fresh crystals containing solvent molecules were used in measurements.
11B NMR spectra of solutions of compounds in dmso-d6 were recorded with a Bruker AC 200 spectrometer at a frequency of 64.297 MHz using BF3·Et2O as an external standard.
X-ray powder diffraction studies of crystals 1·2CH3CN were carried out on a Bruker D8 Advance X-ray diffractometer at the Shared Research Center of the Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences. The measurements were performed using CuKα radiation in low-background cuvettes with a substrate of an oriented silicon single crystal in the 2θ angle range of 5°–80° with a step of 0.01125°. To obtain diffraction patterns, the samples were carefully triturated in an agate mortar. Before the measurements, the samples were dried to constant weight to remove solvent molecules. X-ray powder diffraction patterns of compound 1·2CH3CN are shown in Figure S1. The data obtained verify the purity of the compound.
X-ray diffraction studies of single crystal 1·2CH3CN were performed with a Bruker Apex DUO diffractometer (MoKα radiation, respectively); crystal 2·2CH3CN was studied using a Bruker Smart Apex II diffractometer (MoKα radiation). The structures were solved by the SHELXT method [52] and refined by the full-matrix least squares method against F2 of all data using SHELXL-2014 [53] and OLEX2 [54] software. Nonhydrogen atoms were found on difference Fourier maps and refined with anisotropic displacement parameters. The positions of hydrogen atoms were calculated and included in the refinement in isotropic approximation by the riding model with the Uiso(H) = 1.5Ueq(C) for methyl groups and 1.2Ueq(C) for the other atoms, where Ueq(C) are equivalent thermal parameters of parent atoms. Crystal data, details of data collection, and results of structure refinement are summarized in Table S1. The crystallographic data were deposited with the Cambridge Crystallographic Data Center as supplementary publications under CCDC nos. 2126248 and 2153860. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures (accessed on 17 June 2022). Molecular views of compounds are shown in Figures S2 and S3.

3. Results and Discussion

Here, we studied the reactions of gold(III) complexes [Au(L)Cl2]+ containing chelating N,N-ligands (L = bipy, phen) with the boron cluster anions. Earlier, it was found that iron(III) and cobalt(III) salts react with [BnHn]2− anions (n = 10, 12) in the presence of bipy and phen, giving metal(II) compounds [55] with the boron clusters as counterions or even with substituted derivatives of the closo-decaborate anion with OH or Phen substitutes [56,57]. In the case of less reactive [B12H12]2−, it was possible to isolate the cobalt(III) complex [Co(phen)3][B12H12]NO3 [44].
First, we carried out reactions of [Au(L)Cl2][BF4] with the [B10H10]2− and [B12H12]2− anions in acetonitrile or acetonitrile/water solutions. However, it was found that both boron cluster anions reduce gold(III) to Au0 decomposing to oxidoborates.
(Et3NH)2[B10H10] or (Ph4P)2[B12H12] + [Au(L)Cl2][BF4] → Au0↓ + oxidoborates (L = bipy, phen)
The reaction solutions became black for a few seconds and a thin layer of gold formed on the flask wall, indicating that a gold mirror reaction took place. 11B NMR spectra of the reaction solutions showed the only peak at +20 ppm related to oxidoborates. In the IR spectra, a broad band at 1300–1200 cm−1 is also observed assigned to ν(BO) of oxidoborates. No bands were found around 2500 cm−1, which is a typical range for ν(BH).
Then, we studied the reactions of [Au(L)Cl2][BF4] with [B20H18]2− in acetonitrile and found that in such a case, gold(III) complexes [Au(L)Cl2]2[B20H18] (1: L = bipy, 2: L = phen) precipitate immediately as solvates [Au(L)Cl2]2[B20H18]·2CH3CN (1·2CH3CN or 2·2CH3CN). The complexes start to precipitate from the reaction solutions as dark orange needles (1·2CH3CN) or prisms (2·2CH3CN) as soon as solutions of reagents were mixed in acetonitrile.
(Ph4P)2[B20H18] + [Au(L)Cl2][BF4] → [Au(L)Cl2]2[B20H18]↓
Successful formation of the gold(III) complexes with the [B20H18]2− anion is most probably due to a lower reduction ability of the macropolyhedral boron cluster compared to [BnHn]2− (n = 10, 12) boron clusters.
A crystallographically independent part of the orthorhombic and triclinic unit cells of complexes 1·2CH3CN (Pbca) and 2·2CH3CN (P-1) contains the [Au(L)Cl2]+ cationic complex, half an anion, and a solvate molecule of acetonitrile, thus having the composition of [Au(Bipy)Cl2]2[B20H18]∙2CH3CN or [Au(Phen)Cl2]2[B20H18]∙2CH3CN. The anion in both cases also realizes the trans-configuration. The metal atom of the cations realize the square geometry with the gold(III) atom situated in the center of the AuCl2N2 polyhedron (the shift in metal atom from the center is equal to 0.042(3) Å and 0.043(3) Å, respectively). The Au–N and Au–Cl distances are 2.016(8)–2.064(7) Å and 2.265(5)–2.278(4) Å for 1, and 2.051(7)–2.060(6) Å and 2.270(3)–2.283(3) Å for 2, respectively. In the structures of 1∙2CH3CN and 2∙2CH3CN, additional intermolecular interactions of the gold(III) atom can be observed (Figure 1). These are the B–H...Au interaction with the anion (r(Au...B8) = 3.89(1) Å, AuHB = 138.1(6)°, and NAuH = 72.4(2)–91.2(2)° for 1 and r(Au...B9) = 3.55(1) Å, AuHB = 123.7(5)°, and NAuH = 73.4(2)–93.9(2)° for 2) and a long Au...Cl bond (r(Au-Cl) = 3.406(5) Å, AuClAu = 88.2(2)°, and NAuCl = 82.8(2)–87.7(2)°) in 1 and Au…Au bond (r(Au-Au) = 3.586(4) Å and AuAuN = 86.6(2)–102.6(2)°) in 2. Crystal packings of both compounds are shown in Figures S4 and S5. One of the equatorial BH groups interacts with the gold(III) atom in both structures.
In the IR spectra of complexes 1∙2CH3CN and 2∙2CH3CN, a strong splitting of the band of stretching vibrations ν(BH) is observed near 2500 cm−1, which is explained by weak interactions found in the structure. A narrow intensive band of bending vibrations of the BH group with respect to the boron cage δ(BBH) is observed near 1030 cm−1. Bands ν(CN) assigned to CH3CN molecules are observed near 2300 cm−1. In addition, bands corresponding to coordinated Bipy and Phen ligands are observed in the region of 1600–700 cm−1.
At room temperature, complexes 1∙2CH3CN and 2∙2CH3CN are stable both in DMF solutions (at least for few days) and as solids (for some weeks) following our experimental data. We did not expose it to higher temperatures; however, based on our previous data for closely related compounds, we can expect them to show reasonable thermal stability. Note that cobalt and nickel compounds of the general formula [ML6][B10H10] (M = Co, Ni; L = DMF, H2O, 1/2N2H4) were used for low-temperature synthesis of metal borides [58,59,60,61]; they contain solvent molecules that can be easily removed when heating. Thermal stability data of gold complexes obtained here could be interesting because gold complexes contain metal in a more oxidized form (gold(III)), and in the presence of boron clusters that act as reducing agents, the obtained compounds should be more power-consuming compounds.

4. Conclusions

We studied the reactions of gold(III) complexes [Au(L)Cl2]+ (L = bipy, phen) with hydridoborate anions [B10H10]2−, [B12H12]2−, and the macropolyhedral hydridoborate anion [B20H18]2−. The first gold(III) complexes with a hydridoborate cluster anion [Au(L)Cl2]2[B20H18] (L = bipy, phen) were isolated and characterized. In the structures of the compounds, the B–H...Au interactions were observed above the plane of the square-planar AuN2Cl2 coordination polyhedron.

Supplementary Materials

The following are available online at www.mdpi.com/article/10.3390/inorganics10070099/s1, Figure S1: Calculated (orange) and experimental (black) X-ray powder diffraction patterns of complex 1·2CH3CN, Figure S2: Molecular view of 1∙2CH3CN in representation of atoms with thermal ellipsoids (p = 50%), Figure S3: Molecular view of 2∙2CH3CN in representation of atoms with thermal ellipsoids (p = 50%), Figure S4: Crystal packing of 1∙2CH3CN, Figure S5: Crystal packing of 2∙2CH3CN, Table S1: Crystal structure data and refinement details for 1·2CH3CN and 2·2CH3CN.

Funding

This work was supported by the Ministry of Science and Higher Education of the Russian Federation as part of the State Assignment of the Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences in the field of fundamental research. The X-ray diffraction study was carried out using the equipment of the Centre for Molecular Composition Studies of the A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences. The authors thank the Ministry of Science and Higher Education of the Russian Federation.

Conflicts of Interest

The authors declare no conflict of interest.

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Inorganics 10 00099 g001 550
Figure 1. Gold(III) intermolecular interactions in the crystal of 2∙2CH3CN (a) and 2∙2CH3CN (b).
Figure 1. Gold(III) intermolecular interactions in the crystal of 2∙2CH3CN (a) and 2∙2CH3CN (b).
Inorganics 10 00099 g001
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Avdeeva, V.V.; Vologzhanina, A.V.; Kubasov, A.S.; Akhmadullina, N.S.; Shishilov, O.N.; Malinina, E.A.; Kuznetsov, N.T. Gold(III) Complexation in the Presence of the Macropolyhedral Hydridoborate Cluster [B20H18]2−. Inorganics 2022, 10, 99. https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070099

AMA Style

Avdeeva VV, Vologzhanina AV, Kubasov AS, Akhmadullina NS, Shishilov ON, Malinina EA, Kuznetsov NT. Gold(III) Complexation in the Presence of the Macropolyhedral Hydridoborate Cluster [B20H18]2−. Inorganics. 2022; 10(7):99. https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070099

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Avdeeva, Varvara V., Anna V. Vologzhanina, Alexey S. Kubasov, Nailya S. Akhmadullina, Oleg N. Shishilov, Elena A. Malinina, and Nikolay T. Kuznetsov. 2022. "Gold(III) Complexation in the Presence of the Macropolyhedral Hydridoborate Cluster [B20H18]2−" Inorganics 10, no. 7: 99. https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070099

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