Intramolecularly Coordinated Group 14 and 15 Chalcogenites

Article pubs.acs.org/Organometallics

Intramolecularly Coordinated Group 14 and 15 Chalcogenites Barbora Mairychová, Tomás ̌ Svoboda, Milan Erben, Aleš Růzǐ čka, Libor Dostál,* and Roman Jambor* Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, CZ-532 10, Pardubice, Czech Republic S Supporting Information *

ABSTRACT: The synthesis of N→M intramolecularly coordinated group 14 and 15 chalcogenites is reported. The N→Sn intramolecularly coordinated organotin(IV) carbonate L(Ph)SnCO3 (1), where L is the N,C,N-chelating ligand 2,6(Me2NCH2)2C6H3−, reacts with SO2 and SeO2 to provide the organotin(IV) sulfite L(Ph)SnSO3 (4) and selenite [L(Ph)SnSeO3]2 (5), respectively. Treatment of [LSbO]2 (2) and [LBiO]2 (3) with SeO2 provided the organoantimony and bismuth selenites LSbSeO3 (6) and [LBiSeO3]3 (7), respectively. Compounds 5−7 are rare examples of mixed element oxides with well-defined stoichiometry MSeO3 (M = Sn, Sb, Bi). Compounds 4−7 were characterized by means of elemental analyses, 1 H, 13C, 77Se, and 119Sn NMR spectroscopies, IR spectroscopy, and single-crystal X-ray diffraction analysis.

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INTRODUCTION

combining bismuth and another p-block metal were also reported.9 Surprisingly, while materials based on the combination of SnO2, Sb2O3, or Bi2O3 with either p-block or transition metal oxides are intensively studied,10 materials involving the combination of SnO2, Sb2O3, or Bi2O3 with oxides of group 16 elements are a practically unexplored field.11 Recent studies, however, suggested that the latter materials are good NO sensors or catalysts for oxidation reactions.11 Recently, it was shown that N→M intramolecularly coordinated organometallic oxides [{2,6-(Me2NCH2)2C6H3}(Ph)Sn(μ-O)]2, [{2,6-(Me2NCH2)2C6H3}Sb(μ-O)]2, and [{2,6-(Me2NCH2)2C6H3}Bi(μ-O)]2 easily absorb CO2 to provide the corresponding monomeric organometallic carbonates {2,6-(Me2NCH2)2C6H3}(Ph)SnCO3, {2,6(Me2NCH2)2C6H3}SbCO3, and {2,6-(Me2NCH2)2C6H3}BiCO3 (Chart 1) containing the carbonate group in terminal position.12 This evoked the question whether similar reactions will proceed with oxides of group 16 elements under formation of molecular mixed oxides with well-defined stoichiometry. As part of a comprehensive study on intramolecularly coordinated organometallic oxides of type [L(Y)MO]2 (M = Sn, Sb, Bi, Y = Ph or lone pair, L = N,C,N-coordinating pincer-

Organometallic oxides have attracted much interest because of their application as catalysts in industry. 1 While the homometallic oxides have chemical and physical features that make them important in modern materials chemistry,1 recent research has come to focus on the properties and utility of heterometallic systems.2 Recent developments have occurred in the field of heterobimetallic oxides not only for their catalytic properties3 but also due to the possibility to design new inorganic−organic hybrid materials, which is currently one of the mainstream challenges in the field of advanced materials science.4 The combination of inorganic and organic components at a molecular level enables preparation of mixed organometallic oxides with well-defined stoichiometry of two different elements, which can improve mechanical, thermal, optical, electrical, or magnetic properties of the resulting materials. In recent years, there has been considerable interest in organotin and organoantimony oxides due to their applications in material science or as catalysts.5,6 In contrast, the chemistry of mixed organotin and organoantimony oxides is less extensive. Heterobimetallic tin-oxo arsonates, stannasiloxanes, tellurastannoxanes, and tin−aluminum sulfides, the precursors for materials with specific properties, were prepared.7,8 Studies dealing with the synthesis of organometallic compounds © 2013 American Chemical Society

Received: October 12, 2012 Published: January 3, 2013 157

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Chart 1

Scheme 1. Synthesis of the Organotin Sulfite (4) and Selenite (5)

type ligands 2,6-(Me2NCH2)2C6H3−),12 we report here the synthesis of N→M intramolecularly coordinated mixed organometallic oxides of group 14/15 and 16 elements. The N→Sn intramolecularly coordinated organotin(IV) carbonate L(Ph)SnCO3 (1) reacts with SO2 and SeO2 to give the mixed oxides L(Ph)SnSO3 (4) and [L(Ph)SnSeO3]2 (5), respectively. Treatment of [LSbO]2 (2) and [LBiO]2 (3) with SeO2 provided mixed oxides LSbSeO3 (6) and [LBiSeO3]3 (7). In contrast, reactions of 2 and 3 with SO2 yielded ill-defined materials only, and reactions of 1−3 with TeO2 were not successful as well.

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RESULTS AND DISCUSSION The bubbling of an excess of SO2 through the CH2Cl2 solution of 1 provided the organotin sulfite L(Ph)SnSO3 (4), a rare example of a mixed oxide with the stoichiometry SnSO3 (see Scheme 1). Single crystals of 4 suitable for X-ray diffraction analysis were obtained from a saturated CHCl3 solution by slow evaporation of solvent, and the molecule of water was cocrystallized during this growth to yield 4·H2O. The presence of the H2O molecule does not affect the structure of 4, and there are no hydrogen bonds in the molecular structure. The molecular structure of 4·H2O and selected bond lengths and angles are shown in Figure 1, and the crystallographic data are given in Table S1. The molecular structure of 4·H2O displays an almost planar SnO2S core with a coordination of the sulfite moiety as a terminal ligand in a chelating fashion. This binding mode of the sulfite is unknown for main group metal compounds, and to our knowledge there are few examples with a terminally bonded sulfite group reported up to now for transition metals.13 Structurally characterized organometallic sulfites usually possess

Figure 1. ORTEP view of 4·H2O. The thermal ellipsoids are drawn with 50% probability. Hydrogen atoms are omitted for clarity. Selected bond distances (Å) and angles (deg): Sn1−O1 2.118(3), Sn1−O2 2.124(2), Sn1−N1 2.486(2), Sn1−N2 2.493(2), S1−O3 1.457(2), S1−O1 1.574(2), S1−O2 1.581(2), O1−Sn1−O2 66.57(7), O1− Sn1−N1 78.36(7), O1−Sn1−N2 144.18(7), N1−Sn1−N2 131.68(7).

the sulfite entity in a bridging position to provide polymeric structures.14 The sulfite SO3 moiety is bonded to the tin atom by two oxygen atoms as a terminal ligand, providing a four-membered SnSO2 ring. The Sn1−O1 and Sn1−O2 bond lengths are similar (2.117(3) and 2.124(2) Å), proving nearly symmetrical coordination of the sulfite group, and indicate the presence of Sn−O covalent bonds (∑cov(Sn,O) = 2.03 Å)15 in 4·H2O, respectively. Comparison of the S−O bond lengths within the sulfite group revealed a significant difference between the 158

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the axial positions and two nitrogen and oxygen atoms define the equatorial plane. The intracyclic Se−O−Sn angles vary between 121.80(2)° and 130.16(3)°, and the O−Sn−O angle is 87.39(11)°. According to a classification scheme recently introduced for eight-membered rings, 5 adopts a G-type arrangement.17 This well-defined dimeric structure of 5 contrasts with related triorganotin selenite [(Ph3Sn)2O3Se], consisting of polymers containing two types of tin centers.18 The intramolecular N→Sn coordination in 5 is retained in CDCl3 solution, resulting in an AX-type 1H NMR resonance at δA 3.23 and δX 4.29 for the diastereotopic CH2N protons and two resonances at δ 2.13 and 2.39 for the NCH3 protons. The 119 Sn NMR spectrum of 5 revealed a signal at δ −270.7 that is consistent with a hexacoordinated tin atom.17 The presence of a selenite moiety in 5 was also established by the 77Se NMR spectroscopy, where a signal at δ 1334 was found. In contrast to 5, treatment of 2 with SeO2 provided welldefined monomeric organoantimony selenite LSbSeO3 (6), a rare example of a mixed oxide with stoichiometry SbSeO3 (Scheme 2). The molecular structure of 6 and selected bond lengths and angles are shown in Figure 3, and the crystallographic data are given in Table S1. The molecular structure of 6 displays an almost planar SbO2Se core with a coordination of the selenite moiety as a terminal ligand in an O,O′-chelating fashion. This binding mode of the selenite group is practically unknown for both main group and transition metals since the selenite ligand acts as an O,O,O′- or O,O′,O″-bonded bridge, linking the metal atoms in an oligomeric or polymeric structure.19 The selenite SeO3 moiety is bonded to the antimony atom by two oxygen atoms as a terminal ligand, providing a fourmembered SbSeO2 ring. The Sb1−O1 and Sb1−O2 bond lengths are similar (2.106(3) and 2.115(3) Å) and indicate the presence of Sb−O covalent bonds (∑cov(Sb,O) = 2.03 Å)15 in nearly symmetrically coordinated selenite. The comparison of the Se−O bond lengths within the selenite group revealed a significant difference in the bond lengths between the terminal Se1−O3 (1.615(3) Å) and those coordinated to the antimony atom (Se1−O1 = 1.752(3), Se1−O2 = 1.744(3) Å). The L ligand is coordinated in a tridentate fashion to the central Sb1 atom (Sb1−N1 = 2.539(3) Å and Sb1−N2 = 2.557(3) Å) and provide strong support for the stabilization of the terminal coordination of the selenite moiety. The geometry of the antimony atom can be described as a tetragonal pyramid, where the carbon atom is situated in the axial position and two nitrogen and oxygen atoms define a distorted equatorial plane. The structure of 6 is retained in CDCl3 solution, and the existence of the intramolecular N→Sb coordination provided an AX-type 1H NMR resonance at δA 3.28 and δX 4.42 for the diastereotopic CH2N protons and two resonances at δ 2.05 and 2.60 for the NCH3 protons. The presence of the selenite moiety in 6 was also established by 77Se NMR spectroscopy, where a signal at δ 1376 was found. Finally, treatment of 3 with SeO2 yielded organobismuth selenite [LBiSeO3]3 (7), a rare example of a mixed oxide with stoichiometry Bi3Se3O9 (Scheme 2). The molecular structure of 7 and selected bond lengths and angles are shown in Figure 4, and the crystallographic data are given in Table S1. The molecular structure of 7 showed that the selenite moieties form a complex with organobismuth fragments [LBi]. Three organobismuth fragments are connected through the bridging selenito −O,O,O′ group, providing the central ring with the stoichiometry Bi3Se3O9. Interestingly, each selenite

terminal S1−O3 (1.457(2) Å) bond and those coordinated to tin (S1−O1 = 1.574(2), S1−O2 = 1.581(2) Å). The Sn−N bond lengths (2.486(2) and 2.493(2) Å) suggest the presence of a strong Sn←N interaction, and as a consequence, the geometry of the tin atom can be described as a strongly distorted octahedron, where both carbon atoms are situated in axial positions and two nitrogen and oxygen atoms define the equatorial plane. Elemental analysis, NMR data, and IR spectra of 4 did not, however, show the presence of water and indicate that the water molecule was cocrystallized during the growth of the single crystals. The 119Sn NMR spectrum of 4 revealed a signal at δ −285.6 in CDCl3 solution, which is consistent with the hexacoordinate tin atom.16 The presence of N→Sn coordination in 4 is reflected by observation of an AX-type 1H NMR resonance at δA 3.30 and δX 4.22 for the diastereotopic CH2N protons and two resonances at δ 2.18 and 2.42 for the NCH3 protons. Treatment of 1 with SeO2 yielded organotin selenite [L(Ph)SnSeO3]2 (5), a rare example of a mixed oxide with stoichiometry Sn2Se2O6 (Scheme 1). The molecular structure of 5 and selected bond lengths and angles are shown in Figure 2, and the crystallographic data are given in Table S1.

Figure 2. Molecular structure of 5 together with selected bond lengths (Å) and angles (deg): Sn1−O2a 2.052(3), Sn1−O1 2.069(3), Sn1− N1 2.498(3), Se1−O3 1.633(3), Se1−O1 1.721(3), Se1−O2 1.731(3), O2a−Sn1−O1 87.39(11), C1−Sn1−C13 138.14(15), O1−Sn1−N1 164.69(11), C1−Sn1−N1 74.23(13), O3−Se1−O1 102.65(14), O3−Se1−O2 104.01(14), O1−Se1−O2 99.03(13).

The molecular structure of 5 showed that two bridging selenito −O,O′ groups connect two organotin fragments [L(Ph)Sn], providing an eight-membered ring with the stoichiometry Sn2Se2O4. The comparison of the Se−O bond lengths within the selenite group revealed a significant difference in the bond lengths between the terminal Se1−O3 (1.633(3) Å) and those coordinated to both tin atoms (Se1− O1 = 1.721(3), Se1−O2 = 1.731(3) Å). All Sn−O and Se−O bond lengths that are involved in the eight-membered ring are as expected and fall in the range of a single covalent bond (∑cov(Sn,O) = 2.03 Å; ∑cov(Se,O) = 1.79 Å).15 The Sn−N bond lengths (2.498(3) and 2.887(4) Å) suggest the presence of medium strong Sn−N interactions, and as a consequence, the geometry of the tin atom can be described as a strongly distorted octahedron, where both carbon atoms are situated in 159

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Scheme 2. Synthesis of the Organoantimony (6) and Organobismuth Selenite (7)

Figure 3. ORTEP view of 6. The thermal ellipsoids are drawn with 50% probability. Hydrogen atoms are omitted for clarity. Selected bond distances (Å) and angles (deg): Sb1−O1 2.106(3),Sb1−O2 2.115(3), Sb1−N1 2.539(3), Sb1−N2 2.557(3), Se1−O3 1.615(3), Se1−O2 1.744(3), Se1−O1 1.752(3), O1−Sb1−O2 71.12(10), O1− Sb1−C1 92.97(13), O1−Sb1−N1 74.97(10), N1−Sb1−N2 128.17(10), O3−Se1−O2 106.84(16), O3−Se1−O1 105.22(15), O2−Se1−O1 89.22(12).

Figure 4. Molecular structure of 7 together with selected bond lengths (Å) and angles (deg): Bi1−O6 2.334(7), Bi1−O1a 2.562(5), Bi1−O1 2.562(5), Bi1−N1a 2.613(6), Bi1−N1 2.613(6), Se1−O1 1.687(6), Se1−O1a 1.687(6), Se1−O2 1.702(8), O6−Bi1−O1a 149.99(12), O6−Bi1−O1 149.99(12), O6−Bi1−N1a 78.84(14), O6−Bi1−N1 78.84(14), O1a−Bi1−O1 59.9(2), N1a−Bi1−N1 135.8(3).

six-coordinated central Bi atom with strongly distorted pentagonal pyramidal geometry. The 1H NMR spectrum of 7 revealed the presence of a broad signal at δ 2.81 for CH2N protons and δ 4.30 for the NCH3 protons. The 1H NMR spectrum recorded at 220 K, however, did not show any decoalescence of these broad signals, suggesting the existence of fast fluxional behavior of 7 in CDCl3 solution even at low temperatures. The presence of a selenite moiety in 7 was also established by 77Se NMR spectroscopy, where a signal at δ 1392 was found.

moiety SeO3 coordinates two Bi atoms, while each Bi atom is coordinated by three oxygen atoms originating from two different SeO3 groups. One selenite group coordinates a Bi atom in a bidentate fashion to provide a four-membered BiSeO2 ring (Bi1−O1 = 2.562(5), Bi2−O3 2.525(5), and Bi3− O5 2.591(5) Å), while the remaining oxygen atom of the SeO3 moiety forms a bridge with the neighboring Bi atom (Bi2−O2 = 2.353(8), Bi3−O4 2.281(6), and Bi1−O6 2.334(7) Å). All Se−O bond lengths are nearly identical (range of Se2−O4 1.684(7) to Se1−O2 1.702(8) Å) and fall within the range typical for a single covalent bond (∑cov(Se,O) = 1.74 Å).15 The L ligand is coordinated in a tridentate fashion to the central Bi atoms (range of Bi−N is 2.601(6) to 2.612(6) Å) and defines a

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CONCLUSION We have demonstrated that the NCN-chelating ligand L can be used for the stabilization of different N→M intramolecularly 160

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62%), mp 213−216 °C. Anal. Calcd for C12H19O3N2SbSe: C, 32.7; H, 4.4. Found: C, 32.9; H, 4.1. 1H NMR (500 MHz, CDCl3): δ 2.05 (s, 6H, CH3), 2.60 (s, 6H, CH3), 3.28 (AX system, 2H, CH2), 4.42 (AX system, 2H, CH2), 7.08 (d, 2H, ArH), 7.24 (t, H, ArH). 13C NMR (125.76 MHz, CDCl3): δ 43.0 (CH3), 49.0 (CH3), 63.4 (CH2), 125.6 (C(3,5), 130.2 (C(4)), 145.9 (C (2,6)), 152.9 (C1). 77Se NMR (95 MHz, CDCl3): δ 1376 ppm. IR (ν, cm−1): 904vs, 717m, 703s, 436s. Synthesis of [{2,6-(Me2NCH2)2C6H3}BiSeO3]3 (7). Solid SeO2 (0.02 g, 0.21 mmol) was added to a THF (10 mL) solution of 3 (0.09 g, 0.106 mmol), and the resulting mixture was stirred for 12 h. After the filtration, the solvent was evaporated to provide a solid residue. This residue was washed with hexane (15 mL) to remove starting compound 3 and free ligand L. The white powder was dried to yield an analytically pure compound, 7 (yield 58 mg, 51%), mp 187 °C−dec. Anal. Calcd C12H19O3N2BiSe: C, 27.3; H, 3.6. Found: C, 27.5; H, 3.4. 1H NMR (500 MHz, CDCl3): δ 2.81 (12H, s, (CH3), 4.30 (4H, s, CH2), 7.47 (t, 1H, ArH), 7.66 (d, 2H, ArH). 13C NMR (125.76 MHz, CDCl3): δ 47.0 (CH3), 68.3 (CH2), 128.2 (C(3,5)), 129.4 (C(4)), 153.0 (C(2,6)), (C(1)) not found. 77Se NMR (95 MHz, CDCl3): δ 1392 ppm. IR (ν, cm−1): 792m, 725vs, 441s. Crystallography. Single crystals of 4 suitable for X-ray diffraction analysis were obtained from a saturated CHCl3 solution by slow evaporation of solvent, and the molecule of water was cocrystallized from air during this process (evaporation under a rubber septum) to give 4·H2O. Single crystals of compounds 5−7 were obtained by slow evaporation of saturated CHCl3 (5) or CH2Cl2 (6 and 7) solutions, respectively. The X-ray data (Table S1) for colorless crystals of 4·H2O−7 were obtained at 150 K using an Oxford Cryostream lowtemperature device on a Nonius KappaCCD diffractometer with Mo Kα radiation (λ = 0.71073 Å), a graphite monochromator, and the ϕ and χ scan mode. Data reductions were performed with DENZOSMN.20 The absorption was corrected by integration methods.21 Structures were solved by direct methods (Sir92)22 and refined by full matrix least-squares based on F2 (SHELXL97).23 Hydrogen atoms were mostly localized on a difference Fourier map; however, to ensure uniformity of the treatment of the crystal, all hydrogen atoms were recalculated into idealized positions (riding model) and assigned temperature factors of Hiso(H) = 1.2Ueq(pivot atom) or of 1.5Ueq for the methyl moiety with C−H = 0.96, 0.97, and 0.93 Å for methyl, methylene, and hydrogen atoms in the aromatic rings, respectively. The phenyl ring in the structure of 4·H2O is highly disordered; the best model has been achieved by a splitting of four C and H atoms into two positions with unequal intensity. Further treatment of the thermal ellipsoid for atom C17 was unsuccessful. There is an additional problem within this structure: the presence of additional maxima around the special position attributable to a water molecule, which was placed with half-occupancy. The residual water originating from air does not seem to interact with the SnSO3 unit. There is disordered solvent (dichlormethane) in the structure of 7. Attempts were made to model this disorder or split it into two positions, but were unsuccessful. PLATON/SQUEZZE24 was used to correct the data for the presence of disordered solvent. A potential solvent volume of 1094 Ǻ 3 was found. A total of 759 electrons per unit cell worth of scattering were located in the void. The calculated stoichiometry of solvent was calculated to be 20 molecules of benzene per unit cell, which results in 756 electrons per unit cell. Crystallographic data for structural analysis have been deposited with the Cambridge Crystallographic Data Centre, CCDC nos. 903801 (4), 903802 (6), 903803 (7), and 903804 (5). Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge CB2 1EY, UK (fax: +44-1223336033; e-mail: [email protected] or www: http://www.ccdc. cam.ac.uk).

coordinated mixed organometallic oxides of group 14/15 and 16 elements with well-defined stoichiometry. Depending on the elements used, we were able to isolate molecular mixed oxides with different stoichiometry: SnSO3 (4), Sn2Se2O6 (5), SbSeO3 (6), and Bi3Se3O9 (7). Furthermore, the monomeric organotin sulfite L(Ph)SnSO3 (4) and the organoantimony selenite LSbSeO3 (6) display a unique terminal coordination mode of both the sulfite and selenite moiety. In contrast, the organotin selenite [L(Ph)SnSeO3]2 (5) possesses a dimeric structure with the bridging selenito −O,O′ group, and the organobismuth selenite [LBiSeO3]3 (7) has a trimeric structure, where the Bi atoms are connected by the bridging selenito −O,O,O′ group.19 The isolation of molecular mixed organoelement oxides 4−7 makes them promising precursors for the preparation of new materials based on a combination of group 14/15 and 16 elements.

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EXPERIMENTAL PART

General Methods. The starting compounds 1−3 were prepared according to the literature.12a,b SeO2 was purchased from Sigma Aldrich. All reactions were carried out under argon, using standard Schlenk techniques. Solvents were dried by standard methods and distilled prior to use. The 1H, 13C, 77Se, and 119Sn NMR spectra were recorded on a Bruker Avance500 spectrometer at 300 K in CDCl3 or C6D6. The 1H, 13C, 77Se, and 119Sn NMR chemical shifts (δ) are given in ppm and referenced to external Me4Sn (119Sn) or Me2Se (77Se). Elemental analyses were performed on a LECO-CHNS-932 analyzer. IR spectra were recorded in the range 4000−400 cm−1 on a Nicolet 6700 FTIR spectrometer using Nujol mull technique. Synthesis of [{2,6-(Me2NCH2)2C6H3}(Ph)SnSO3] (4). SO2 was bubbled through a CH2Cl2 solution (15 mL) of 1 (0.06 g, 0.13 mmol) for 20 min. The solvent was evaporated in vacuo to provide a solid residue. This residue was washed with toluene (10 mL) to remove starting compound 1 and free ligand L. The resulting white powder was dried to give analytically pure compound 4 (yield 0.05 g, 84%), mp 240−243 °C. Anal. Calcd for C18H24N2O3S2SSn (467.16 g/ mol): C, 46.3; H, 5.2. Found: C, 46.2; H, 5.0. 1H NMR (CDCl3, 500.13 MHz): δ 2.18 (s, 6H, CH3), 2.42 (s, 6H, CH3), 3.30 (AX system, 2H, CH2), 4.22 (AX system, 2H, CH2), 7.15−7.50 (m, 6H, ArH), 8.30 (d, 2H, ArH). 13C NMR (CDCl3, 125.77 MHz): δ 44.3 (CH3), 46.2 (CH3), 62.5 (CH2), 126.7 (C (3,5)), 129.0 (C′(3,5)), 130.4 (C(4)), 131.3 (C′(4)), 135.9 (C′(2,6)), 136.3 (C′(1)), 138.8 (C(1)), 143.1 (C(2,6)). 119Sn NMR (CDCl3, 186.49 MHz): δ −285.6. IR (ν, cm−1): 1122vs, 1030m, 1007s, 666vs, 542s. Synthesis of [{2,6-(Me2NCH2)2C6H3}(Ph)SnSeO3]2 (5). Solid SeO2 (0.03 g, 0.23 mmol) was added to a CH2Cl2 (15 mL) solution of 1 (0.10 g, 0.23 mmol), and the resulting suspension was stirred for 4 h. Filtration followed by evaporation provided a solid residue. This residue was washed with toluene (10 mL) to remove starting compound 1 and free ligand L. The resulting white powder was dried to yield an analytically pure compound, 5 (yield 0.10 g, 89%), mp 206−207 °C. Anal. Calcd for C18H24N2O3S2SeSn (514.05 g/mol): C, 42.1; H, 4.7. Found: C, 41.8; H, 4.8. 1H NMR (CDCl3, 500.13 MHz): δ 2.13 (s, 6H, CH3), 2.39 (s, 6H, CH3), 3.23 (AX system, 2H, CH2), 4.29 (AX system, 2H, CH2), 7.17 (d, 2H, ArH), 7.39 (d, 1H, ArH), 7.51 (m, 3H, ArH), 8.05 (d, 2H, ArH). 13C NMR (CDCl3, 125.77 MHz): δ 44.4 (CH3), 46.4 (CH3), 62.8 (CH2), 127.0 (C (3,5)), 129.1 (C′(3,5)), 130.4 (C(4)), 131.2 (C′(4)), 136.0 (C′(2,6)), 137.6 (C′(1)), 140.8 (C(1)), 144.1 (C(2,6)). 77Se NMR (CDCl3, 95.38 MHz): δ 1334.1, 119Sn NMR (CDCl3, 186.49 MHz): δ −270.7. IR (ν, cm−1): 898vs, 882m, 767s, 755s, 729vs, 700s, 455m-sh, 447m. Synthesis of [{2,6-(Me2NCH2)2C6H3}SbSeO3] (6). Solid SeO2 (0.07 g, 0.64 mmol) was added to a THF (10 mL) solution of 2 (0.21 g, 0.32 mmol), and the resulting suspension was stirred for 12 h. After the filtration, the solvent was evaporated to give a solid residue. This residue was washed with hexane (15 mL) to remove starting compound 2 and free ligand L. The resulting white powder was dried to provide an analytically pure compound, 6 (yield 174 mg,

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ASSOCIATED CONTENT

S Supporting Information *

Table S1, discussion of IR spectra of 4−7, and further details of the structure determination of compounds 4−7, including atomic coordinates, anisotropic displacement parameters, and 161

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Organometallics

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected], [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors wish to thank the Grant Agency of the Czech Republic (project no. P106/10/0443) and The Ministry of Education of the Czech Republic for financial support.

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REFERENCES

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