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Coordination Chemistry of Anticrowns. Synthesis and Structures of Double-Decker Sandwich Complexes of the Three-Mercury Anticrown (o‑C6F4Hg)3 with Halide Anions Containing and Not Containing Coordinated Dibromomethane Molecules Kirill I. Tugashov, Dmitry A. Gribanyov, Fedor M. Dolgushin, Alexander F. Smol’yakov, Alexander S. Peregudov, Marija Kh. Minacheva, Irina A. Tikhonova, and Vladimir B. Shur* A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Street 28, 119991 Moscow, Russia S Supporting Information *

ABSTRACT: The interaction of the three-mercury anticrown (o-C6F4Hg)3 (1) with [PPh4][BF4] in methanol at room temperature leads to fluoride anion transfer from BF4− to 1 with the formation of a fluoride complex, [PPh4]{[(o-C6F4Hg)3]2F}, having a double-decker sandwich structure. The fluoride ion in this unique adduct is disposed between the mutually parallel planes of the central nine-membered rings of the anticrown units and cooperatively coordinated by all six Hg sites. The iodide anion also forms a double-decker sandwich in the interaction with 1, but this sandwich, [PPh4]{[(o-C6F4Hg)3]2I}, has a wedgeshaped geometry. The reaction of 1 with [nBu4N]Cl in dibromomethane at −15 °C affords a complex, [nBu4N]{[(oC6F4Hg)3]2Cl(CH2Br2)2}, containing one chloride anion and two coordinated CH2Br2 species per two molecules of 1. A similar bromide complex of 1, containing two coordinated CH2Br2 moieties, has also been synthesized and structurally characterized. Both compounds represent wedge-shaped double-decker sandwiches wherein the halide anion is simultaneously bonded to all Hg centers of the anticrown molecules. The dibromomethane species in the isolated adducts are also arranged in the space between the mercuramacrocycles. One of these species is coordinated by each of its bromine atoms to a single Hg site of the adjacent macrocycle while the other interacts by only one bromine atom with a Hg center of the neighboring molecule of 1.

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polydecker wedge-shaped sandwiches [(···1···X···)n]n− (X = Br, I) in the crystal. Interestingly, every halide anion in the synthesized adducts proved to be cooperatively bonded by all six Hg atoms of two neighboring mercuramacrocycle rings, i.e., the coordination number of the halogen atoms in 8 and 9 is equal to six. Chloride anion, in contrast to bromide and iodide anions, reacted with an equimolar amount of 1 in ethanol to afford the complex {[(o-C6F4Hg)3]3Cl2}2− (10), containing two halide anions per three molecules of the anticrown.35 For this complex, the triple-decker sandwich structure [1···Cl···1··· Cl···1]2− was proposed but an X-ray diffraction study of the isolated compound could not be carried out. Subsequently, a large amount of information on different aspects of coordination, supramolecular, and catalytic chemistry of macrocycle 1 has been accumulated, and at the present time

INTRODUCTION

The coordination chemistry of anticrowns has received considerable development over the last two decades owing to a remarkable ability of these charge-reverse analogues of crown ethers and related species to efficiently bind various anions and neutral Lewis bases with the formation of complexes of unprecedented structures (see the reviews in refs 1−7 and papers cited in refs 8−34). Especially effective among the presently described anticrowns are polymercuramacrocycles with electron-withdrawing perfluorohydrocarbon1,3−5,8−34 and o-carborane2,7 backbones (see, e.g., macrocycles 1−7 in Chart 1), strongly increasing the Lewis acidity of the Hg centers. The first indications of the possibility of using perfluorinated polymercuramacrocycles as anticrowns were obtained in 1991, when it was reported35,36 that cyclic trimeric perfluoro-ophenylenemercury (o-C6F4Hg)3 (1), containing three Hg atoms in a planar nine-membered ring,37,38 readily coordinates bromide and iodide anions to yield the 1:1 complexes {[(oC6F4Hg)3]Br}− (8) and {[(o-C6F4Hg)3]I}− (9), forming © XXXX American Chemical Society

Received: March 22, 2016

A

DOI: 10.1021/acs.organomet.6b00231 Organometallics XXXX, XXX, XXX−XXX

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MNDO method39 revealed the possibility of the existence of a similar sandwich for X = I. Later, the complexes [(1)2X]− (X = I, Br, Cl, F), containing two molecules of 1 per halide anion, were detected in aqueous acetonitrile solutions of macrocycle 1 and ammonium halides NH4X by nanoelectrospray mass spectrometry and it was suggested that the observed species constitute the aforementioned double-decker sandwiches.40 In the present article, the first data on the synthesis, isolation, and X-ray structures of the sandwich complexes of such a type are reported. In the case of chloride and bromide anions, the resulting adducts contain also the coordinated molecules of CH2Br2, which was used as a solvent. For the double-decker sandwich complexes of o-carboranylmercury anticrown 4 with chloride, bromide, and iodide anions, see ref 41.

Chart 1

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RESULTS AND DISCUSSION The fluoride complex of macrocycle 1 was obtained on studying the complexation of 1 with tetrafluoroborate anion. The experiments were conducted in methanol solution at room temperature with the use of [PPh4][BF4] as a BF4− source. It turned out, however, that no tetrafluoroborate complexes of 1 are produced under these conditions; instead, the fluoride anion transfer from BF4− to 1 occurs in the course of the reaction to give BF3(MeOH) as an intermediate and a complex, [PPh4]{[(o-C6F4Hg)3]2F} (11), containing one fluoride ion per two anticrown molecules. 2(o‐C6F4 Hg)3 + [PPh4][BF4] + MeOH 1

→ [PPh4]{[(o‐C6F4 Hg)3 ]2 F} + BF3(MeOH)

this three-mercury anticrown is the most studied among compounds of such a type. The polydecker sandwich complexes 8 and 9 include the corresponding double-decker sandwiches [1···X···1]− as fragments which might, in principle, correspond to individual compounds. However, our earlier attempts to synthesize these unusual adducts by the interaction of 1 with halide anions failed. In the meantime, quantum-chemical calculations by the

11 11

According to B NMR spectra, the initially formed BF3(MeOH) reacts further with an excess of methanol to afford B(OMe)3 (δ +19.1 ppm) and HBF4 (δ −0.9 ppm).42−44 Complex 11 was isolated from the solution in an analytically pure state in 75% yield and fully characterized. The roomtemperature 199Hg NMR spectrum of 11 in acetone-d6 ([11]0 =

Figure 1. 19F NMR spectrum of complex 11 in acetone-d6. B


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Figure 2. ORTEP representation of the molecular structure of the anionic part of complex 11 with thermal ellipsoids drawn at the 50% probability level. Selected bond lengths (Å): Hg(1)−F(1) 2.6140(2), Hg(2)−F(1) 2.6196(2), Hg(3)−F(1) 2.6468(2).

Figure 3. Intramolecular Hg···C contacts in the structure of 11 between the Hg centers of one of the anticrown units and the carbon atoms of the aromatic CC bonds of the other anticrown moiety. The coordination of the fluoride anion with the Hg sites is not shown here for clarity. Selected distances (Å): Hg(1)−C(7A) 3.447(4), Hg(1)−C(8A) 3.562(4), Hg(2)−C(13A) 3.295(4), Hg(2)−C(14A) 3.299(4), Hg(3)−C(2A) 3.567(4), Hg(3)−C(1A) 3.584(4).

4 × 10−2 mol L−1) shows a multiplet at δ −276 ppm (relative to external Ph2Hg in Py) shifted downfield by 55 ppm with respect to the corresponding signal of neat 1. The 19F NMR spectrum of 11 in acetone-d6 ([11]0 = 1.5 × 10−2 mol L−1) is typical for an AA′XX′ spin system (see Figure 1) and exhibits two multiplets of equal intensity at δ(o-F) −120.0 ppm and δ(m-F) −159.8 ppm (relative to CFCl3 as an external standard). The spectrum also contains satellite signals due to the coupling of the 199Hg nucleus (natural abundance 16.84%) with the 19F atoms (3JF−Hg = 520 Hz, 4JF−Hg = 165 Hz) as well as a singlet of the coordinated fluoride anion at δ −32.5 ppm with the corresponding satellites (1JF−Hg = 255 Hz). In accordance with the stoichiometry of the complex, the intensity ratio of the aforementioned multiplets and singlet is equal to 12:12:1. The 19F NMR spectrum of free 1 in acetone-d6 is also typical for an AA′XX′ system but differs markedly in its parameters (δ(o-F) −120.9 ppm, δ(m-F) −159.5 ppm, 3JF−Hg = 473 Hz, 4JF−Hg = 130 Hz) from those of 11. An X-ray diffraction study of complex 11 has shown that it has a double-decker sandwich structure (Figure 2). The fluoride anion in this unique sandwich is located between the mutually parallel planes of the central nine-membered rings of the anticrown units and simultaneously coordinated by all six Hg centers. The Hg(1)−F(1), Hg(2)−F(1), and Hg(3)−F(1) distances in the centrosymmetric molecule of 11 are 2.6140(2),

2.6196(2), and 2.6468(2) Å and all these distances are significantly shorter than the sum of the van der Waals radii of mercury (1.73−2.00 Å,45,46 2.1 Å47) and fluorine (1.4 Å47) atoms. Close Hg−F distances (2.5567(5) and 2.6544(8) Å) were observed earlier in a complex of a fluoride anion with an ocarboranylmercury anticrown, (o-C2B10H8Me2Hg)4 (6), containing four Hg atoms in the ring (see Chart 1). The fluoride ion in this 1:1 complex, [Me4N]{[(o-C2B10H8Me2Hg)4]F}, is situated in the plane formed by four Hg sites of the mercuracycle and is bonded to all these Lewis acidic centers.48 In the two previously synthesized complexes featuring a Hg− F−B motif, the Hg−F separations were 2.589(2) Å49 and 2.618(3) and 2.646(4) Å50 (1JHg−F = 135.2 and 122.0 Hz respectively). An interesting structural feature of complex 11 is also a noticeable deviation of two of three C6F4 rings in each macrocycle unit from the mean plane of the appropriate central nine-membered cycle (the corresponding dihedral angles are 11.9, 11.1, and 1.7°), and the deviations of these rings in one macrocycle moiety and in the other point away from the fluoride anion and from one another (see Figure 2). This result can be explained by the small size of the fluoride ion and, as a consequence, by an electrostatic repulsion between the anticrown molecules in 11 which bear a partial negative charge due to their coordination with F−. An additional effect could be C


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Figure 4. ORTEP representation of the molecular structure of the anionic part of complex 13 with thermal ellipsoids drawn at the 50% probability level. Both coordinated CH2Br2 molecules in 13 are disordered over three positions with 0.85/0.85/0.30 occupancies; the minor component is omitted for clarity. Selected bond lengths (Å): Hg(1)−Cl(1) 3.043(3), Hg(2)−Cl(1) 3.066(3), Hg(3)−Cl(1) 3.145(3), Hg(4)−Cl(1) 3.035(3), Hg(5)−Cl(1) 3.092(3), Hg(6)−Cl(1) 3.193(3), Hg(3)−Br(2) 3.486(3), Hg(4)−Br(1) 3.422(3), Hg(5)−Br(4) 3.601(3).

The stacks are arranged along the b crystal axis. The mean planes of the adjacent Hg3C6 rings in the stack are parallel to one another and are separated by 3.21 Å. The mutual arrangement of these juxtaposed rings in the stack corresponds to a staggered conformation, and their centroids are laterally shifted relative to one another by 3.6 Å. As result of such an arrangement, one of the C6F4 rings of each anticrown unit in the stack is located nearly over the center of the neighboring mercuramacrocycle moiety and for this reason cannot deviate essentially from the mean plane of the central Hg3C6 cycle, in contrast to two other C6F4 rings (see above). A chloride complex of analogous composition, [AsPh4]{[(oC6F4Hg)3]2Cl} (12), was synthesized in 75% isolated yield by the interaction of 1 with [AsPh4]Cl at room temperature in CH2Cl2 (1:Cl− = 2:1). The complex precipitates from the reaction solution as a fine white powder poorly soluble in organic solvents, which did not allow us to record satisfactory NMR spectra of this compound. For the same reason, good single crystals of complex 12 also could not be grown despite our efforts. A different chloride complex of macrocycle 1 was obtained on an addition of a solution of [nBu4N]Cl in CH2Br2 to a solution of 1 in the same solvent at −15 °C (Cl−:1 = 2:1). It turned out that under such conditions colorless crystals of the complex [nBu4N]{[(o-C6F4Hg)3]2Cl(CH2Br2)2} (13), containing one chloride anion and two coordinated CH2Br2 molecules per two macrocycle units, are formed in the course of the reaction. These crystals proved to be suitable for an X-ray diffraction study. Figure 4 shows the structure of 13. Like 11, the anionic part of complex 13 represents a double-decker sandwich but, in contrast to 11, this sandwich has a wedge-shaped geometry (the dihedral angle between the mean planes of the central ninemembered rings of the macrocycles is 30.6°). The chloride anion in 13 is disposed between the planes of two molecules of 1 and coordinated with the Hg centers of each of them in an η3 fashion. The Hg−Cl separations in this fragment of the complex span the range 3.035(3)−3.193(3) Å (average 3.10 Å), and all of these separations are considerably shorter than the

exerted by steric interactions between the atoms of the anionic and cationic parts of the complex. The mean planes of the central Hg3C6 cycles in 11 are separated by 3.33 Å, and the fluoride anion is equally distant (1.665 Å) from these planes. The coordination environment at the fluoride ion is close to octahedral (the Hg−F−Hg angles are equal to 180 and 85.86(1)−94.15(1)°). The mutual orientation of the molecules of 1 in 11 corresponds to a staggered conformation. The small size of the fluoride anion leads also to a considerable shortening of the intramolecular Hg···C distances in 11 between the Hg centers of one of the anticrown units and the nearest aromatic carbon atoms of the central Hg3C6 ring of the other molecule of 1 (Figure 3). These distances range from 3.295(4) to 3.584(4) Å (average 3.46 Å) and are all noticeably shorter than the corresponding van der Waals separation (the van der Waals radius of carbon atom is 1.7 Å47). Thus, one may assume that not only the fluoride anion but also the CC bonds of both Hg3C6 rings in complex 11 are involved in the interaction with the Hg atoms of the anticrown moieties. The Hg(1)···Hg(2A), Hg(1A)···Hg(2), Hg(2)···Hg(3A), Hg(2A)··· Hg(3), Hg(1)···Hg(3A), and Hg(1A)···Hg(3) distances in the complex span the range 3.813(1)−3.852(1) Å (average 3.84 Å) and are markedly shorter than the corresponding van der Waals separation as well. Somewhat longer Hg···C and Hg···Hg distances between the mercury and carbon atoms belonging to Hg3C6 cycles of two different molecules of 1 are observed in the structure of the centrosymmetric cofacial dimers formed by one of the polymorphs of 1 in the crystal (Hg···C 3.443−3.650 Å, average 3.51 Å; Hg···Hg 3.811−4.093 Å, average 3.97 Å).51,52 The molecules of the macrocycle in these dimers, in contrast to those in 11, have a planar structure. The distance between the mean planes of the central Hg3C6 cycles in the dimer is 3.35 Å. In the crystal, the anionic parts of the molecules of 11 are associated into extended ladderlike stacks (see Figure 2S in the Supporting Information) due to shortened (in comparison to the sum of the van der Waals radii) intermolecular Hg···Hg and Hg···C contacts between the neighboring molecules of the adduct (Hg···Hg 3.506(1) Å, Hg···C 3.395(5)−3.704(5) Å). D


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Figure 5. ORTEP representation of the molecular structure of the anionic part of complex 16 with thermal ellipsoids drawn at the 50% probability level. The CH2Br2 molecule, in which the sole Br atom participates in the coordination, is disordered over two positions with 0.7/0.3 occupancies; the minor component is omitted for clarity. Selected bond lengths (Å): Hg(1)−Br(1) 3.1224(9), Hg(2)−Br(1) 3.2016(9), Hg(3)−Br(1) 3.2832(9), Hg(4)−Br(1) 3.1566(9), Hg(5)−Br(1) 3.2189(9), Hg(6)−Br(1) 3.3226(9), Hg(3)−Br(2S) 3.493(1), Hg(4)−Br(1S) 3.560(1), Hg(5)−Br(4S) 3.573(2).

[nBu4N]{[(o-C6F4Hg)3]2Cl} (15), analogous in its composition to 12. Unfortunately, as in the case of 12, crystals of 15 suitable for an X-ray diffraction study could not be grown despite our numerous attempts. The 199Hg NMR spectrum of complex 15 in acetone-d6 at 233 K ([15]0 = 4 × 10−2 mol L−1) shows a broad signal at δ −195 ppm, but at 295 K a signal of the 199Hg resonance disappears from the spectrum due, apparently, to the existence of fast (on the NMR time scale) equilibria of dissociation/ complexation under such conditions. The room-temperature 19 F NMR spectrum of 15 in acetone-d6 ([15]0 = 1.5 × 10−2 mol −1 L ), like that of 1, exhibits two multiplets of equal intensity at δ(o-F) −119.9 ppm and δ(m-F) −160.1 ppm and the corresponding satellite signals (3JHg−F = 505 Hz). The interaction of 1 with [nBu4N]Br in CH2Br2 was carried out under the same conditions as in the case of the aforementioned synthesis of chloride complex 13 from 1 and [nBu4N]Cl. As a result of the reaction, a bromide complex of an analogous composition, viz. [ nBu 4N]{[(o-C 6F 4 Hg) 3]2 Br(CH2Br2)2} (16), was produced. According to an X-ray analysis, complex 16 is isostructural with 13 (see Figure 5) and also has a geometry of a wedge-shaped double-decker sandwich (the dihedral angle between the mean planes of the central Hg3C6 cycles of the macrocycles is 32.6°). The bromide anion in 16, like the chloride ion in 13, is cooperatively coordinated by all six Hg sites of two molecules of 1. The Hg− Br bond lengths in this coordination fragment of 16 (3.1224(9)−3.3226(9) Å; average 3.22 Å) are within the van der Waals separation and are comparable with those (3.132(1)−3.309(1) Å; average 3.21 Å) in the previously synthesized double-decker sandwich complex [MePPh3]{[(oC2B10H8Me2Hg)3]2Br}·2Me2CO·2H2O (17) of anticrown 4 with bromide anion.41 In this complex, however, the central Hg3C6 cycles of the anticrown units, as in the case of the corresponding chloride adduct, are parallel to one another. The Hg−Br distances in the aforementioned bromide complex 8 (3.071−3.610 Å; average 3.25 Å), having a wedge-shaped

corresponding van der Waals distance (the van der Waals radius of chlorine atom is 1.8 Å47). In the earlier synthesized double-decker sandwich complex of chloride anion with ocarboranylmercury anticrown (o-C2B10H8Me2Hg)3 (4), containing three Hg atoms in the cycle, the Hg−Cl distances are in the range 3.146(6)−3.177(5) Å (average 3.16 Å).41 However, in this sandwich, [PPN]{[(o-C2B10H8Me2Hg)3]2Cl} (14), in contrast to 13, the central Hg3C6 cycles of the anticrown molecules are parallel to each other. In the 1:1 complex of the four-mercury anticrown (o-C2B10H10Hg)4 (5) with Cl−, the Hg−Cl bond lengths are 2.944(2) Å.53 Markedly longer Hg−Cl distances (3.089(6)−3.388(8) Å; average 3.25 Å) were observed in the structure of the bipyramidal dichloride complex [PPh4]2{[(CF3)2CHg]5Cl2}, which was isolated from the reaction of the five-mercury anticrown [(CF3)2CHg]5 (2) with [PPh4]Cl in ethanol solution.54 The chloride anion in complex 13 is arranged at a distance of 2.34 Å from the mean plane of the central Hg3C6 ring of the Hg(1)Hg(2)Hg(3) macrocycle and at a distance of 2.40 Å from the mean plane of the Hg3C6 ring of the Hg(4)Hg(5)Hg(6) macrocycle. In contrast to the case for 11, octahedral coordination at the halide anion in 13 is strongly distorted (the Hg−Cl−Hg bond angles range from 69.2(1) to 156.8(1)°). Like the chloride anion, the CH2Br2 molecules in complex 13 are also located in the space between the anticrown moieties. As seen from Figure 4, one of these molecules is bonded by each of its bromine atoms to a single Hg center of the neighboring anticrown unit, whereas the other is coordinated by only one bromine atom to a single Hg site of the adjacent macrocycle. The Hg−Br distances in these coordination fragments of 13 are significantly shorter than the corresponding van der Waals distance (the van der Waals radius of bromine atom is 1.9 Å47) and are equal to 3.422(3)−3.601(3) Å (average 3.50 Å). Complex 13 is thermally unstable and readily loses both CH2Br2 molecules on drying under vacuum at room temperature to form the corresponding chloride complex E


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([20]0 = 4 × 10−2 mol L−1) displays a broad signal at δ −121 ppm. In the spectrum of 11, a signal of the mercury resonance at 233 K in acetone-d6 ([11]0 = 4 × 10−2 mol L−1) is observed at −281 ppm. Thus, on transition from fluoride complex 11 to chloride complex 15 and then to the corresponding bromide and iodide complexes 18 and 20, the signal of the 199Hg resonance at 233 K is increasingly shifted downfield (from −281 to −195 ppm and then to −172 and −121 ppm). Such a trend in alteration of chemical shifts suggests an increase in stability of halide complexes of 1 in acetone solution in the order F− < Cl− < Br− < I−, which is in accord with the aforementioned ESI MS data for complexes [(1)2X]− (X = F, Cl, Br, I).40 At 295 K, a signal of the mercury resonance in the spectrum of 20, as in the case of 15 and 18, is not manifested. The room-temperature 19F NMR spectra of complexes 19 and 20 in acetone-d6 ([19]0 = [20]0 = 1.5 × 10−2 mol L−1) are identical and show two multiplets at δ(o-F) −119.5 ppm and δ(m-F) −160.0 ppm of equal intensity as well as satellite signals (3JHg−F = 495 Hz). The structure of complex 19 is shown in Figure 6. Like 13 and 16, the complex has also a wedge-shaped double-decker

polydecker sandwich structure,35 and in the bipyramidal dibromide complex [PPh4]2{[(CF3)2CHg]5Br2} of anticrown 2 (3.229(3)−3.453(3) Å; average 3.34 Å)55 are also close to those in 16. A 1:1 complex of anticrown 5 with Br− is characterized by the Hg−Br separations of 3.028(5)−3.087(5) Å (average 3.06 Å).56 The distances between the bromide anion and the mean planes of the central Hg3C6 rings of two mercuramacrocycle moieties in complex 16 are 2.49 Å in the case of the Hg(1)Hg(2)Hg(3) macrocycle and 2.53 Å in the case of the Hg(4)Hg(5)Hg(6) macrocycle. Octahedral coordination at the halide anion in 16, as in 13, is strongly distorted (the Hg−Br− Hg bond angles are in the range 66.14(2)−153.92(3)°). The bonding of the CH2Br2 species in complex 16 is analogous to that of CH2Br2 in 13. One of these species is coordinated by each of its two bromine atoms to a single Hg center of the adjacent macrocycle, while in the other molecule of CH2Br2, only one bromine atom is involved in the bonding to a Hg site of the neighboring mercuramacrocycle molecule. The Hg−Br distances observed here are considerably longer than those between the bromide anion and the Hg atoms and amount to 3.493(1)−3.573(2) Å (average 3.54 Å). Drying of 16 under vacuum at room temperature for 3 h leads to complete loss of both coordinated CH2Br2 molecules and to the formation of the complex [ n Bu 4 N]{[(oC6F4Hg)3]2Br} (18) according to elemental analysis. The 199 Hg NMR spectrum of 18 in acetone-d6 at 233 K ([18]0 = 4 × 10−2 mol L−1) is characterized by a broad signal at δ −172 ppm; however, at 295 K, as in the case of 15, no signal of the 199 Hg resonance is observed in the spectrum. The roomtemperature 19F NMR spectrum of 18 in acetone-d6 ([18]0 = 1.5 × 10−2 mol L−1), like those of 1 and 15, exhibits two multiplets of equal intensity (δ(o-F) = −119.8 ppm and δ(m-F) = −160.1 ppm) and the corresponding satellite signals (3JHg−F = 505 Hz). Attempts to obtain single crystals of this compound were unsuccessful. The C6F4 rings in each macrocycle moiety of complexes 13 and 16 somewhat deviate from the mean plane of the appropriate central Hg3C6 cycle (the corresponding dihedral angles are 4.3−12.1° (average 7.1°) in 13 and 3.1−10.6° (average 6.1°) in 16), and again these deviations in one macrocyclic fragment of the complex and in the other point away from the halide anion and from one another. The observed distortion of the planarity of 1 in complexes 13 and 16 can be due to their wedge-shaped structure, leading to a strong approach of the anticrown units to each other in the sharp part of the edge and, as a consequence, to an increase in a steric repulsion between them. An additional repulsive effect could be caused by the presence of the dihalomethane molecules in the space between the macrocycles in the adducts. The reaction of 1 with [PPh4]I in CH2Cl2 at room temperature (1:I− = 2:1) results in the formation of colorless crystals of an iodide complex, [PPh4]{[(o-C6F4Hg)3]2I} (19), not containing CH2Cl2 molecules and analogous in its composition to compounds 11, 12, 15, and 18 according to elemental analysis and X-ray diffraction data. The complex is insufficiently soluble in conventional organic solvents, which did not allow us to record a satisfactory 199Hg NMR spectrum. A similar but more soluble iodide complex, [nBu4N]{[(oC6F4Hg)3]2I} (20), was isolated as a fine white powder from the reaction of 1 with [nBu4N]I at −15 °C in CH2Br2. The 199 Hg NMR spectrum of this adduct in acetone-d6 at 233 K

Figure 6. ORTEP representation of the molecular structure of the anionic part of complex 19 with thermal ellipsoids drawn at the 50% probability level. Selected bond lengths (Å): Hg(1)−I(1) 3.2606(17), Hg(2)−I(1) 3.3212(18), Hg(3)−I(1) 3.3886(17), Hg(4)−I(1) 3.4104(17), Hg(5)−I(1) 3.3530(18), Hg(6)−I(1) 3.3629(17).

sandwich geometry (the dihedral angle between the mean planes of the central nine-membered rings of the macrocycles is 31.1°). The iodide anion in 19, like the halide anions in 11, 13, and 16, is cooperatively bonded by all Hg sites of the anticrown units. The Hg−I distances in 19 range from 3.2606(17) to 3.4104(17) Å (average 3.35 Å), and all these distances are within the corresponding van der Waals separation (the van der Waals radius of iodine atom is 2.1 Å47). Somewhat shorter Hg− I bond lengths (3.2492(5)−3.2728(5) Å; average 3.26 Å) were previously observed in the double-decker sandwich complex of the three-mercury anticrown 4 with iodide anion.41 The central H g 3 C 6 rings in this sandwich, [Li(H 2 O) 4 ]{[(oC2B10H8Me2Hg)3]2I}·2MeCN, as in 14 and 17, are parallel to each other. In the aforementioned iodide complex 9, having a wedge-shaped polydecker sandwich structure, the Hg−I distances span the range 3.331−3.487 Å (average 3.43 Å),36 and in the diiodide complexes [AsPh4]2{[(o-C2B10H10Hg)4]I2} and [K(dibenzo-18-crown-6)]2{[(o-C2B10H8Me2Hg)4]I2}, they F


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Organometallics are equal to 3.304(1)−3.774(1) Å (average 3.42 Å)57 and 3.335(3) and 3.438(4) Å,58 respectively. The Hg−I separations in the bipyramidal diiodide complex [PPh4]2{[(CF3)2CHg]5I2} are 3.395(1)−3.546(1) Å (average 3.48 Å).39 The deviations of the C6F4 rings in each macrocycle unit of complex 19 from the mean plane of the corresponding central Hg3C6 cycle are in the range 2.3−7.3° (average 4.4°). Octahedral coordination at the halide anion in 19 is again strongly distorted (the Hg−I−Hg bond angles range from 63.44(3)° to 160.57(5)°). The distances from the iodide ion to the mean planes of the central Hg3C6 rings of two anticrown units in the complex are close to each other (2.66 Å in the case of the Hg(1)Hg(2)Hg(3) macrocycle and 2.70 Å in the case of Hg(4)Hg(5)Hg(6) macrocycle). The Hg−C bond distances in the macrocycle moieties of complexes 11, 13, 16, and 19 are unexceptional (2.073(4)− 2.093(4) Å in 11, 2.068(16)−2.102(14) Å in 13, 2.055(9)− 2.095(8) Å in 16, and 2.04(3)−2.12(2) Å in 19). The C−Hg− C bond angles, as in free 1, are close to 180° (171.72(16)− 176.05(17)° in 11, 170.2(7)−174.5(6)° in 13, 172.5(3)− 175.1(4)° in 16, and 172.7(9)−176.2(11)° in 19). The mutual orientation of the mercury macrocycles in 13 and 16, as in 11, is close to a staggered conformation, while in 19 this orientation is closer to an eclipsed conformation. The anionic parts of complexes 13, 16, and 19 also form extended stacks in the crystals due to shortened intermolecular Hg···Hg and Hg···C contacts between the adjacent sandwich moieties (13, Hg···Hg 3.910(1)−4.080(1) Å, Hg···C 3.49(1)− 3.79(1) Å; 16, Hg···Hg 3.903(1)−4.086(1) Å, Hg···C 3.45(1)− 3.91(1) Å; 19, Hg···Hg 3.669(2) and 3.977(2) Å, Hg···C 3.34(3)−3.75(3) Å). The stacks are disposed along the a crystal axis, but in contrast to 11, they are not of ladderlike character. The central Hg3C6 rings of the neighboring macrocycles in the stacks of complex 19 are virtually parallel to one another (see Figure 2S in the Supporting Information) and are separated by 3.33 Å. The stacks formed by complexes 13 and 16 are characterized by alternating distances between the mutually parallel Hg3C6 rings of the neighboring macrocycles (3.45 and 3.55 Å in 13 and 3.44 and 3.59 Å in 16). The lateral shifts of the centroids of these juxtaposed Hg3C6 rings relative to each other also alternate in the stack (0.94 and 3.71 Å in 13; 0.86 and 3.79 Å in 16). In complex 19, the corresponding relative lateral shift of the centroids is equal to 2.43 Å. The mutual orientation of the adjacent macrocycles in the stacks of complexes 13 and 16 is close to a staggered conformation, while in the case of 19 close to an eclipsed conformation is realized.

these cases the resulting adducts contain two coordinated dihalomethane species along with the coordinated halide anion. The synthesis of iodide sandwich 19 was conducted in CH2Cl2 solution, but the isolated product, in contrast to 13 and 16, does not contain the solvent molecules in its composition. It should be noted that according to quantum-chemical calculations39 the molecules of macrocycle 1 in its doubledecker sandwich complex with iodide anion should be parallel to each other, although in reality, as mentioned above, the synthesized compound 19 has a wedge-shaped geometry. This discrepancy is apparently due to packing effects. The first dihalomethane complex with an anticrown was obtained in our laboratory by the interaction of the aforementioned five-mercury macrocycle 2 with BF4− ion followed by the recrystallization of the resulting product from CH 2 Cl 2 . 59 The isolated adduct {[(CF 3 ) 2 CHg] 5 (BF 4 )(CH2Cl2)}− contains one BF4− anion and one CH2Cl2 molecule which are located on different sides of the metallacycle plane. According to X-ray crystallography, the BF4− ion in this adduct behaves as a tetradentate ligand and is bonded to the Hg sites of 2 in an η5:η2:η1:η1 fashion (Hg−F 2.980(9)−3.266(10) Å), whereas the CH2Cl2 species is coordinated with 2 by a single chlorine atom, in an η5 fashion (Hg−Cl 3.538(4)−3.700(4) Å; average 3.64 Å). Recently, the synthesis of a 1:1 dichloromethane complex of macrocycle 1, not containing any other ligands, was briefly reported.32 The CH2Cl2 molecule forms here two comparatively short Hg−Cl contacts of an η1 type (3.351(2) and 3.604(3) Å) formed by two chlorine and two Hg atoms. For macrocycle 1, complexes with 1-halonaphthalenes of 1:1 composition have also been described.60 The complexes form extended binary stacks in the crystal wherein the molecules of 1 alternate with the haloarene species. The isolated adducts exhibit relatively short Hg−Carom distances (3.28−3.43 Å), suggesting secondary Hg−π interactions. An additional contribution to the bonding can be made by the coordination of the halogen atoms with the Hg sites. For example, in the case of one of the independent molecules of the 1-chloronaphthalene complex, the chlorine atom interacts with each neighboring mercuramacrocycle unit in an η1 fashion (Hg−Cl 3.500(12) and 3.419(14) Å), while in the case of 1-bromo- and 1-iodonaphthalene adducts the η3 coordination of the halogen atom with one of the adjacent mercuracycles in the stack is realized (Hg−Br 3.565(2)−3.843(2) Å, average 3.74 Å; Hg−I 3.626(13)−3.836(14) Å, average 3.76 Å). Thus, even inert aromatic halogen atoms are able to be involved in the bonding to the Hg centers of 1. The results obtained impressively illustrate an extremely high affinity of perfluorinated mercury anticrowns toward various electron-donating species.

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CONCLUSION The results of our study demonstrate the ability of macrocycle 1 to form double-decker sandwich complexes with halide anions. According to X-ray diffraction, the obtained chloride, bromide, and iodide sandwiches 13, 16, and 19 have a wedgeshaped structure, whereas in the fluoride sandwich 11 the central Hg3C6 cycles of the anticrown molecules are parallel to one another. In all sandwiches, the halide anion is bonded to the Hg centers of each macrocycle unit in a η3 fashion, as a result of which the coordination number of the halogen atom turns out to be equal here to six. The synthesized fluoride adduct 11 is the first example of a sandwich complex of fluoride anion with an anticrown. The syntheses of chloride and bromide sandwiches 13 and 16 were carried out with the use of CH2Br2 as a solvent, and in

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EXPERIMENTAL SECTION

Because of the toxicity of the mercury compounds studied in this work, great care should be exercised during their synthesis, handling, and storage. The starting macrocycle 1 was prepared according to the published procedures.37 Commercial [PPh4]Cl (Aldrich; 98%), [AsPh4]Cl (Sigma; 98%), [nBu4N]Cl (Aldrich; 97%), [nBu4N]Br (Aldrich; 99%), [PPh4]I (Fluka; 99%), [nBu4N]I (Aldrich; 99%), and NaBF4 (purum) were used without additional purification. Solvents were purified by conventional methods and freshly distilled prior to use over calcium hydride (methanol), P2O5 (CH2Cl2, CH2Br2), or LiAlH4 (Et2O) under Ar. The 199Hg NMR spectra were recorded on a Bruker Av-600 instrument using a 0.2 M solution of Ph2Hg in pyridine (δ −791.1 ppm61) as an external standard. The 11B and 19F spectra G


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Organometallics were measured on a Bruker Av-400 instrument using BF3·Et2O and CFCl3 as external standards, respectively. The IR spectra were recorded as Nujol mulls on a Bruker Tensor 37 Fourier spectrometer. Synthesis of [PPh4][BF4]. To a solution of [PPh4]Cl (0.38 g, 1.0 mmol) in water (20 mL) was added upon stirring at room temperature a solution of NaBF4 (0.11 g, 1.0 mmol) in water (4 mL). Immediately, a fine white powder of [PPh4][BF4] began to precipitate. The next day, the precipitated [PPh4][BF4] was filtered off, washed with cold water (6 × 2 mL), and dried at 20 °C under vacuum for 5 h. Yield: 0.33 g (78%). Anal. Calcd for C24H20BF4P: C, 67.64; H, 4.73; F, 17.83. Found: C, 67.78; H, 4.84; F, 17.50. 19F NMR (acetone-d6, δ, ppm): −151.8 (s). 11B NMR (acetone-d6, δ, ppm): −0.9 (s). IR (νBF, cm−1): 1057. Synthesis of Complex 11. To a solution of macrocycle 1 (0.1043 g, 0.1 mmol) in methanol (4 mL) was added at 20 °C a solution of [PPh4][BF4] (0.0216 g, 0.05 mmol) in methanol (5 mL), and the resulting mixture was allowed to stand at room temperature. Within 3 h, colorless crystals of complex 11 began to form on the bottom and the walls of the vessel. After 6 days, the obtained mixture was slowly concentrated to 2 mL and the precipitated crystals of 11 were filtered off, washed with methanol (3 × 0.5 mL) and diethyl ether (2 × 1 mL), and dried at 20 °C under vacuum for 2 h. Yield of 11: 0.0915 g (75%). Anal. Calcd for C60H20F25PHg6: C, 29.41; H, 0.82; F, 19.38. Found: C, 29.22; H, 0.75; F, 19.14. 19F NMR (acetone-d6, δ, ppm): −32.5 (s with satellites, 1JF−Hg = 255 Hz, 1F); −120.0 (m with satellites, 3JF−Hg = 520 Hz, 12F); −159.8 (m with satellites, 4JF−Hg = 165 Hz, 12F). 199Hg NMR (acetone-d6, 233 K, δ, ppm): −281 (m). 199Hg NMR (acetoned6, 295 K, δ, ppm): −276 (m). Synthesis of Complex 12. To a solution of 1 (0.1044 g, 0.1 mmol) in CH2Cl2 (14 mL) was added a solution of [AsPh4]Cl (0.0208 g, 0.05 mmol) in CH2Cl2 (3 mL), and the resulting mixture was kept at room temperature overnight. Within 1 h, a fine white powder of complex 12 began to precipitate. The next day, the reaction mixture was slowly concentrated to 5 mL and the precipitated 12 was filtered off, washed with CH2Cl2 (3 × 1 mL), and dried at 20 °C under vacuum for 2 h. Yield of 12: 0.0942 g (75%). Anal. Calcd for C60H20F24ClAsHg6: C, 28.70; H, 0.80; F, 18.16. Found: C, 28.58; H, 0.92; F, 18.06. Synthesis of Complexes 13 and 15. To a solution of macrocycle 1 (0.1043 g, 0.1 mmol) in CH2Br2 (10 mL) was added at −15 °C a solution of [nBu4N]Cl (0.0140 g, 0.05 mmol) in CH2Br2 (3 mL). Immediately, a white powder began to precipitate and in 5 min the reaction mixture was placed in a freezer (−15 to −20 °C). The next day, the resulting mixture was warmed to room temperature (0.5 h) and the precipitated colorless crystals of complex 13 and a fine white powder (consisting, apparently, of 13 or/and some other chloride dibromomethane complex) were filtered off, washed with CH2Br2 (3 × 1 mL), and dried for 3 h at 20 °C under vacuum. As a result of drying, complex 15 was produced. Yield of 15: 0.0618 g (52% based on the starting 1). Anal. Calcd for C52H36NF24ClHg6: C, 26.35; H, 1.53; F, 19.24. Found: C, 26.23; H, 1.30; F, 19.15. 19F NMR (acetone-d6, δ, ppm): −119.9 (m with satellites, 3JF−Hg = 505 Hz, 12F); −160.1 (m, 12F). 199Hg NMR (acetone-d6, 233 K, δ, ppm): −195 (br). For the Xray diffraction study, the crystals of 13 were not washed and dried under vacuum. Synthesis of Complexes 16 and 18. To a solution of macrocycle 1 (0.1044 g, 0.1 mmol) in CH2Br2 (10 mL) was added at −15 °C a solution of [nBu4N]Br (0.0161 g, 0.05 mmol) in CH2Br2 (2.5 mL). Immediately, a white powder began to precipitate. In 5 min, the reaction mixture was placed in a freezer (−15 to −20 °C). The next day, the resulting mixture was warmed to room temperature (0.5 h) and the precipitated colorless crystals of complex 16 and a fine white powder of the same compound (according to X-ray powder diffraction data) were filtered off, washed with CH2Br2 (3 × 1 mL), and dried under vacuum for 3 h at 20 °C. In the course of drying, the complex lost both coordinated CH2Br2 molecules to afford complex 18. Yield of 18: 0.0984 g (82% based on the starting 1). Anal. Calcd for C52H36NF24BrHg6: C, 25.87; H, 1.50; F, 18.89. Found: C, 25.62; H, 1.72; F, 18.78. 19F NMR (acetone-d6, δ, ppm): −119.8 (m with satellites, 3JF−Hg = 505 Hz, 12F); −160.1 (m, 12F). 199Hg NMR

(acetone-d6, 233 K, δ, ppm): −172 (br). For the X-ray diffraction study, the crystals of 16 were not washed and dried under vacuum. Synthesis of Complex 19. To a solution of 1 (0.1205 g, 0.115 mmol) in CH2Cl2 (15 mL) was added a solution of [PPh4]I (0.0255 g, 0.055 mmol) in CH2Cl2 (2 mL), and the resulting mixture was allowed to stand at room temperature. Within 0.5 h, colorless crystals of complex 19 began to form. After 2 days, the reaction mixture was slowly concentrated to 5 mL and the resulting crystals of 19 were filtered off, washed with CH2Cl2 (5 × 1 mL), and dried at 20 °C under vacuum for 2.5 h. Yield of 19: 0.1074 g (77%). Anal. Calcd for C60H20F24PIHg6: C, 28.17; H, 0.79; F, 17.82. Found: C, 28.28; H, 1.18; F, 17.37. 19F NMR (acetone-d6, δ, ppm): −119.5 (m with satellites, 3JF−Hg = 495 Hz, 12F); −160.0 (m, 12F). Synthesis of Complex 20. To a solution of macrocycle 1 (0.1050 g, 0.1 mmol) in CH2Br2 (10 mL) was added at −15 °C a solution of [nBu4N]I (0.0183 g, 0.05 mmol) in CH2Br2 (2.5 mL). Immediately, a white powder began to precipitate and in 5 min the resulting mixture was placed in a freezer (−15 to −20 °C). The next day, the precipitated white powder of complex 20 was filtered off, washed with CH2Br2 (3 × 1 mL), and dried for 3 h at 20 °C under vacuum. Yield of 20: 0.0807 g (66%). Anal. Calcd for C52H36NF24IHg6: C, 25.38; H, 1.47; F, 18.53. Found: C, 25.64; H, 1.48; F, 18.36. 19F NMR (acetoned6, δ, ppm): −119.5 (m with satellites, 3JF−Hg = 495 Hz, 12F); −160.0 (m, 12F). 199Hg NMR (acetone-d6, 233 K, δ, ppm): −121 (br). X-ray Diffraction Study. Single-crystal X-ray diffraction experiments were carried out with a Bruker SMART APEX II diffractometer (graphite-monochromated Mo Kα radiation, λ = 0.71073 Å, ω-scan technique). The APEX II software62 was used for collecting frames of data, indexing reflections, determining lattice constants, integrating intensities of reflections, scaling, and correcting for absorption, while SHELXTL63 was applied for space group and structure determination, refinements, graphics, and structure reporting. The structures were solved by direct methods and refined by the full-matrix least-squares technique against F2 with anisotropic thermal parameters for all nonhydrogen atoms. The hydrogen atoms were placed geometrically and included in the structure factor calculations in the riding motion approximation. Crystallographic data for complexes 11, 13, 16, and 19 are presented in Table 1S in the Supporting Information.

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ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.6b00231. Main experimental and crystallographic parameters for compounds 11, 13, 16, and 19, projections of the coordinated halide anion and one of the macrocycles onto the central Hg3C6 ring plane of the other macrocycle in complexes 11, 16, and 19, fragments of crystal packing of complexes 11 and 19, and the powder pattern for complex 16 (PDF) Crystallographic data of compounds 11, 13, 16, and 19 (CIF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail for V.B.S.: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the Russian Foundation for Basic Research (project codes 16-03-00749 and 13-03-01176). Structural studies were supported by the Russian Science Foundation (project code 14-13-00884). H


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Organometallics

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