Intramolecularly Coordinated Stannanechalcogenones - American

Oct 14, 2011 - Roman Jambor*. ,† ... Pardubice, Czech Republic ... Research Institute for Organic Syntheses, Rybitvi 296, CZ 533 54 Rybitvн, Czech ...
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Intramolecularly Coordinated Stannanechalcogenones: X-ray Structure of [2,6-(Me2NCH2)2C6H3](Ph)SndTe   Barbora Mairychova,† Libor Dostal,† Ales Ru zicka,† Michal Fulem,‡ Kvetoslav Ru zicka,‡ Antonín Lycka,§ and ,† Roman Jambor* †

Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentska 95, CZ-532 10, Pardubice, Czech Republic ‡ Department of Physical Chemistry, Institute of Chemical Technology, Technicka 5, CZ-166 28 Prague 6, Czech Republic § Research Institute for Organic Syntheses, Rybitvi 296, CZ 533 54 Rybitví, Czech Republic

bS Supporting Information ABSTRACT: The treatment of an intramolecularly coordinated organotin(IV) dichloride, [2,6-(Me2NCH2)2C6H3](Ph)SnCl2 (1), with Li2E (E = S, Se, Te) afforded thermally stable dimeric diarylstannanethione [{2,6-(Me2NCH2)2C6H3}(Ph)Sn(μ-S)]2 (2) and monomeric diarylstannaneselone and -tellurone [{2,6(Me2NCH2)2C6H3}(Ph)SndE] (E = Se (3), Te (4)). Compounds 24 were characterized by means of elemental analyses and 1H, 13C, 77Se, 119Sn, and 125 Te NMR spectroscopy. The molecular structures of 2 and 4 were determined by single-crystal X-ray diffraction analysis. Solution NMR studies revealed dependence of the structure of compounds 2 and 3 on the solvent (C6D6 or CDCl3). In addition, the synthesis of dimeric stannanetellurone [{2,6-(Me2NCH2)2C6H3}(Bu)Sn(μ-Te)]2 (5) showed an influence of the organic group R (R = Bu or Ph) on the structure of diorganotin(IV) tellurides 4 and 5.

’ INTRODUCTION Tin chalcogenides have semiconducting properties with a naturally narrow band gap. Thin films of these compounds are promising materials for the fabrication of mid-IR photodetectors, light-emitting diodes, or diode lasers.1 The investigation of organotin chalcogenides is of current interest, since they have both elements (Sn and either Se or Te) in one molecule and, thus, they can be applied as potential single-source precursors for the deposition of thin layers of tin chalcogenides.2 As the concept of single-source precursors has drawn the attention of many research groups in recent years,3 the organometallic compounds containing the element combination Sn/E (E = S, Se, Te) are known.4 Most of them, however, contain a four-membered motif of the type [Sn(μ-E)]2, leading to high molecular weights and low volatilities, making them unfavorable for the deposition of thin layers.3 For this reason, terminal chalcogenido complexes of the organotin compounds are of current interest. Although compounds containing a double bond between heavier group 14 and 16 elements,5 i.e., heavier congeners of a ketone (called “heavy ketones”), are fascinating synthetic targets, there are only limited examples of their isolation. Two methods have been exploited to stabilize these highly reactive functionalities, since they prevented an oligomerization of SndE terminal bonds. Kinetic stabilization by the use of bulky substituents on group 14 elements has been applied successfully (Chart 1A).5,6 In an r 2011 American Chemical Society

alternative approach, stabilization may be achieved by intramolecular heteroatom coordination (Chart 1B).7 Both methods were successfully applied for the stabilization of stannanethiones and -selones; however, there is still a very limited number of structurally characterized stannanetellurones.7a,8 As part of a comprehensive study on intramolecularly coordinated organotin(IV) compounds of the type Ar(Ph)SnX 2 (X = electronegative substituent, Ar = N,C,N- or O,C,O-coordinating pincer-type ligands [2,6-(Me2NCH2)2C6H3] and [2,6-(MeOCH2)2C6H3], respectively),9 we report here the synthesis of dimeric diarylstannanethione [{2,6-(Me2NCH2)2C6H3}(Ph)Sn(μ-S)]2 (2) and monomeric diarylstannaneselone and -tellurone [{2,6-(Me2NCH2)2C6H3}(Ph)SndE] (E = Se (3), Te (4)). Compounds 24 were characterized by means of elemental analyses and 1H, 13C, 77Se, 119Sn, and 125Te NMR spectroscopy. Molecular structures of 2 and 4 were determined by single-crystal X-ray diffraction analysis. Solution NMR studies revealed dependence of the structure of compounds 2 and 3 on the solvent (C6D6 or CDCl3). In addition, synthesis of the dimeric stannanetellurone [{2,6-(Me2NCH2)2C6H3}(Bu)Sn(μ-Te)]2 (5) showed an influence of the organic group R (R = Bu or Ph) on the structure of diorganotin(IV) tellurides 4 and 5. Received: August 11, 2011 Published: October 14, 2011 5904

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Chart 1

Scheme 1. Synthesis of Compounds 24

’ RESULTS AND DISCUSSION The starting compound L(Ph)SnCl 2 (1), where L is 2, 6-(Me2NCH2)2C6H3, was synthesized according to the literature.10 The treatment of 1 with Li2E (E = S, Se, Te), prepared in situ from Li[BHEt3] and E, yielded the desired intramolecularly coordinated stannanechalcogenones [L(Ph)Sn(μ-S)]2 (2) and [L(Ph)SndE] (E = Se (3), Te (4)) (Scheme 1). Molecular Structures of 2 and 4. Single crystals of [L(Ph)Sn(μ-S)]2 (2) suitable for X-ray diffraction analysis were obtained by slow diffusion from a CH2Cl2 solution. The molecular structure of 2, selected bond lengths, and angles are shown in Figure 1 and the crystallographic data are given in Table 1. The molecular structure of 2 resembles related intramolecularly coordinated organotin(IV) sulfides 4k,7a,7b,11 and is formed as a centrosymmetric dimer with a planar Sn2 S 2 core with both ligands L placed mutually in cis positions with respect to the central Sn 2 S 2 core. Nitrogen atoms are coordinated to the tin atom (range of NSn distances is 2.741(6)3.219(6) Å) in cis position with angles of N1Sn1N2 113.63(16)° and N3Sn2N4 115.21(15)°, respectively. Single crystals of compound 4 suitable for X-ray diffraction analysis were obtained from a toluene/hexane solution at 10 °C. The molecular structure of 4, selected bond lengths, and angles are shown in Figure 2, and the crystallographic data are given in Table 1. The tin atom is five-coordinated and exhibits a distorted square-pyramidal configuration with N1, N2, C1, and C13 atoms being located in equatorial positions and the Te1 atom in the axial position. The bond angles of N1Sn1N2 and C1 Sn1C13 are 148.20(5)° and 108.70(7)°, respectively. The distance of the terminal Te1Sn1 bond (2.6139(2) Å) is

Figure 1. Molecular structure of 2 together with selected bond lengths (Å) and angles (deg): Sn1N1 3.149(6), Sn1N2 2.741(6), Sn2N3 2.815(6), Sn2N4 3.219(6), Sn1S1 2.4591(17), Sn1S2 2.4320(18), N1Sn1N2 113.63(16), N3Sn2N4 115.21(15), Sn1S1Sn2 89.67(6), S1Sn1S2 89.97(6).

comparable to those found in the monomeric stannanetellurone [Bbt(Titp)SndTe] (2.5705 Å)8 and [{CH(SiMe3)C9H6N8}2SndTe] (2.618 Å),7a but smaller than the sum of the covalent radii of Sn (1.40 Å) and Te (1.37 Å).7a Solution NMR Studies of 24. Compound 2 was found to be a sulfido-bridged dimer in C6D6 solution as well, as is evident from 1H, 13C, and 119Sn NMR spectra, where only one set of signals was observed. The 119Sn NMR spectrum shows a single resonance at δ 154.3, shifted downfield compared with starting 1 (δ 241.0).10 The intramolecular NfSn coordination is retained in solution, resulting in an AX-type resonance at δA 2.79 and δX 5.24, with JAX being 23 Hz for the diastereotopic CH2N protons and a singlet resonance at δ 2.15 for the NCH3 protons in the 1H NMR spectrum. This structural rigidity of 2 in solution contrasts with the cis/trans isomerization of related O,C, O-chelated diorganotin sulfides, where two sets of NMR signals having similar chemical shifts were observed (for cis/trans isomerization see Scheme S1 in the Supporting Information).11a The 1H, 13C, 77Se, and 119Sn NMR spectra of compound 3 in the C6D6 revealed two set of signals, in contrast to compound 2. The 119 Sn NMR spectrum showed two resonances at δ 4.7 and 306.0. 5905

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Table 1. Crystal Data and Structure Refinement for 2, 4, and 5 4 3 0.5C7H8

2

5

empirical formula

C36H48N4S2Sn2

C21.5H28N2SnTe

C32H56N4Sn2Te2

color

colorless

yellow

yellow

cryst syst

monoclinic

monoclinic

triclinic

space group

P21/c

P21/c

P1

a [Å]

13.1780(14)

14.1631(6)

9.7301(4)

b [Å]

17.2891(16)

9.4550(5)

9.9550(5)

c [Å]

18.0080(18)

16.7430(6)

10.9500(3)

α [deg] β [deg]

90 114.204(8)

90 98.589(4)

77.494(3) 64.519(2)

γ [deg]

90

90

84.688(4)

Z

4

4

1

μ [mm1]

1.476

2.449

2.891

Dx [Mg m3]

1.488

1.680

1.758

cryst size [mm]

0.41  0.37  0.21

0.47  0.30  0.24

0.34  0.23  0.13

cryst shape

plate

block

plate

θ range [deg] F max./min. [e/Å3]

127.5 0.728/0.938

127.5 0.398/0.644

127.5 1.132/1.086

no. of reflns measd

30 208

22 875

19 413

no. of unique reflns; Rinta

8507, 0.0856

5014, 0.0418

4254,0.0585

no. of obsd reflns [I > 2σ(I)]

5018

4543

3625

no. of params

397

199

181

Sb all data

1.125

0.998

1.128

final Rc [I > 2σ(I)]

0.0515

0.0188

0.0284

wR2c (all data)

0.1149

0.0423

0.0672

Rint = ∑|Fo2  Fo,mean2|/∑Fo2. b GOF = [∑(w(Fo2  Fc2)2)/(Ndiffrs  Nparams)]1/2 for all data, c R(F) = ∑||Fo|  |Fc||/∑|Fo|for observed data, wR(F2) = [∑(w(Fo2  Fc2)2)/(∑w(Fo2)2)]1/2 for all data. a

Scheme 2. Dimerization of Stannaneselone [L(Ph)SndSe] to Selenido-Bridged Dimer [L(Ph)Sn(μ-Se)]2 in C6D6 Solution of 3

Figure 2. Molecular structure of 4 together with selected bond lengths (Å) and angles (deg): Sn1N1 2.4794(17), Sn1N2 2.4836(17), Sn1C13 2.1469(19), Sn1C1 2.1223(18), Sn1Te1 2.6139(2), C13Sn1N1 90.73(6), N1Sn1C1 73.88(6), C1Sn1N2 73.88(6), N2Sn1C13 99.96(6), Te1Sn1C1 136.57(5), Te1Sn1N1 100.12(4), N1Sn1 N2 148.20(5), C1Sn1C13 108.70(7).

The signal at δ 4.7 displays satellites with a large coupling constant 1J(119Sn77Se) = 2965.6 Hz, which is consistent with

the directly bonded SndSe moiety7a,b and defines the presence of the monomeric stannaneselone [L(Ph)SndSe]. The latter, upfield shifted, signal at δ 306.0 also displays satellites due to coupling of 119Sn and 77Se. The value of the coupling constant 1 119 J( Sn77Se) is only 791.0 Hz and corresponds well with the selenido-bridged dimer [L(Ph)Sn(μ-Se)]2.4k,12 The existence of stannaneselone and its dimeric form in C6D6 was also corroborated by the 1H and 77Se NMR spectra. The 1H NMR spectrum revealed an AB-type resonance at δA 2.98 and δB 3.26 for the CH2N protons and two signals at δ 1.57 and 2.31 for the NCH3 protons, which is in accordance with chiral arrangement of the tin atom in the stannaneselone [L(Ph)SndSe] (Scheme 2). The presence of an AX-type resonance at δA 2.65 and δX 5.10 with JAX being 40 Hz for the diastereotopic CH2N protons and a singlet resonance at δ 1.96 for the NCH3 protons in the 1H NMR spectrum 5906

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Table 2. NMR Data of Compounds 24 Measured in CDCl3 and C6D6 1

119

H NMR

δ(CH2) compound 2

form dimer

3 4

CDCl3

2.79/5.24

2.85/4.87

C6D6 2.15

3.64/3.85

dimer

2.65/5.10

monomer

2.98/3.26

CDCl3 2.25

C6D6

CDCl3

154.3

158.5

2.05/2.61

3.62/3.83

1.57/2.31

59.8 306.0

1.96 2.03/2.58

4.7

4.8

156.5

a

dimer monomer

a

δ(CH3)

C6D6

monomer

Sn NMR

2.91/3.20

a

1.63/2.36

a

Not measured due to the instability in CDCl3.

suggests the presence of the selenido-bridged dimer [L(Ph)Sn(μ-Se)]2 (Scheme 2), similarly to compound 2. The 77Se NMR spectrum of 3 also showed two signals at δ 570.9 (stannaneselone) and 43.2 (dimer). The molar ratio of stannaneselone [L(Ph)SndSe] and selenido-bridged dimer [L(Ph)Sn(μ-Se)]2, detected from the 1H NMR spectrum of 3 (20 mg in 0.5 mL of C6D6), is 8:2 (for concentration studies see Table S1 in the Supporting Information). The 1H, 13C, 119Sn, and 125Te NMR spectra of a C6D6 solution of compound 4 revealed one set of signals. The 119Sn NMR spectrum showed a resonance at δ 156.5 with satellites due to coupling of 119Sn and 125Te. The large coupling constant 1J(125Te119Sn) = 7574 Hz is consistent with a directly bonded SndTe moiety7a and defines the presence of the monomeric stannanetellurone [L(Ph)SndTe] in C6D6 solution. The 1H NMR spectrum revealed an AB-type resonance at δA 2.91 and δB 3.20 for the CH2N protons and two signals at δ 1.63 and 2.36 for the NCH3 protons, in accordance with the chiral arrangement of the tin atom in the stannanetellurone [L(Ph)SndTe]. The 125Te NMR spectrum of 4 showed a signal at δ 1393.7. The NMR studies in C6D6 solution showed that compound 2 was a sulfido-bridged dimer [L(Ph)Sn(μ-S)]2, compound 3 exhibited an equilibrium of stannaneselone [L(Ph)SndSe] and its dimeric form [L(Ph)Sn(μ-Se)]2, and compound 4 existed as monomeric stannanetellurone [L(Ph)SndTe]. Further studies were focused on the influence of solvents (C6D6, CDCl3) on the dimerization of intramolecularly coordinated stannanechalcogenones. Effect of the Solvent: Solutions of 2 and 3 in CDCl3. When compound 2 was dissolved in CDCl3, the 1H and 119Sn NMR spectra revealed two set of signals (see Table 2). The 119Sn NMR spectrum showed two resonances at δ 158.5 and 59.8. While the former signal, similar to that found in C6D6 solution, corresponds to the dimeric form [L(Ph)Sn(μ-S)]2, the downfield shifted signal at δ 59.8 defines the presence of the monomeric stannanethione [L(Ph)SndS] in CDCl3 solution. Similarly, the 1H NMR spectrum, in addition to the signals diagnostic for the dimeric form, revealed an AB-type resonance at δA 3.64 and δB 3.85 for the CH2N protons and two signals at δ 2.05 and 2.61 for the NCH3 protons, suggesting the presence of monomeric stannanethione [L(Ph)SndS] (see Table 2; for concentration studies see Table S1 in the Supporting Information). The 1H and 119Sn NMR spectra of compound 3 in CDCl3 solution revealed one set of signals only (see Table 2) and define the presence of the monomeric stannaneselone

Figure 3. Molecular structure of 5 together with selected bond lengths (Å) and angles (deg): Sn1N1 2.983(4), Sn1N2 2.852(4), Sn1Te1 2.7696(3), Sn1Te1a 2.7830(4), N1Sn1N2 112.79(11), Te1 Sn1Te1a 91.69(1), C1Sn1C13 121.81(15).

[L(Ph)SndSe] in CDCl3. The 119Sn NMR spectrum showed a resonance at δ 4.8 with 1 J(119 Sn77 Se) = 2965 Hz (presence of a SndSe moiety), 7a,b and the 1 H NMR spectrum revealed an AB-type resonance at δ A 3.62 and δB 3.83 for the CH2 N protons and two signals at δ 2.03 and δ 2.58 for the NCH 3 protons. Effect of Organic Group R. Since compound 4 exists as the monomeric stannanetellurone [L(Ph)SndTe] both in the solid state and in solution, further studies were focused on the influence of the organic group R (Ph, Bu) on the dimerization process. For this reason, dimeric alkylarylstannanetellurone [L(Bu)Sn(μ-Te)]2 (5) containing a less sterically demanding butyl substituent was prepared. Single crystals of 5 suitable for X-ray diffraction analysis were obtained by slow diffusion from C6D6 solution. The molecular structure of 5, selected bond lengths, and angles are shown in Figure 3, and the crystallographic data are given in Table 1. The molecular structure of 5 is formed as a centrosymmetric dimer with a planar Sn2Te2 core and where both chelating ligands L are placed mutually trans with respect to the central Sn2Te2 core. 5907

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Organometallics The 1H, 13C, and 119Sn NMR spectra of a C6D6 solution of 5 revealed two set of signals. The 119Sn NMR spectrum showed two resonances at δ 104.1 and 291.8. The signal at δ 104.1 displays satellites with a large coupling constant 1J(119Sn125Te) = 7389 Hz, which is consistent with a directly bonded SndTe moiety7a and defines the presence of the monomeric stannanetellurone [L(Bu)SndTe]. The upfield shifted signal at δ 291.8 also displays satellites due to coupling of 119Sn and 125Te. The value of the coupling constant 1J(119Sn125Te) is 1472 Hz and corresponds well with the tellurido-bridged dimer [L(Bu)Sn(μ-Te)]2.4k,12 The existence of stannanetellurone and its dimeric form in C6D6 was also corroborated by the 1H NMR spectrum (see Experimental Part). Volatility Measurements for 24. Compounds 24 were tested as suitable single source precursors, and their volatility and solid heat capacities were measured for this purpose.13,14 The vapor pressures (Table S2 in the Supporting Information) do not exceed 0.15 Pa at 298.15 K and showed low volatility of the studied compounds. The solid heat capacities of 2 and 3 (Table S3) are of importance for the development of group contribution estimation methods where the contributions of groups containing metals are rarely available. In conclusion, thermally stable dimeric diarylstannanethione [L(Ph)Sn(μ-S)]2 (2) and monomeric diarylstannaneselone and -tellurone [L(Ph)SndE] (E = Se (3), Te (4)) were prepared and characterized. Compound 2 is a sulfido-bridged dimer, and compound 4 exists as a monomeric stannanetellurone in C6D6 solution as well as in the solid state. Compound 3, however, exhibited the existence of stannaneselone [L(Ph)SndSe] and its dimeric form [L(Ph)Sn(μ-Se)]2 in C6D6 solution. The influence of the solvent on the dimerization of intramolecularly coordinated stannanechalcogenones 2 and 3 was also studied. While the dimeric form of compound 2 exists in C6D6 solution, both dimeric and mononeric forms of 2 were detected in CDCl3 solution. Compound 3 exists as a monomer and dimer in C6D6 solution, while the existence of monomeric stannaneselone was achieved in CDCl3 solution. As the NMR data of compounds 24 are clearly different from those reported for the non-basestabilized monomeric stannanechalcogenones with a terminal SndE double bond, the presence of the polar single bond Sn+E can be assumed in stannanechalcogenes 24. The positive charge on the tin atom is probably stabilized by two strong SnrN interactions, and thus the presence of the ligand L seems to be crucial for stabilization of monomeric stannanechalcogenones 24. The synthesis of compound 5 showed the influence of the organic group R (R = Bu or Ph) on the structure of stannanetellurones 4 and 5. While compound 4 is monomeric, compound 5, containing the less sterically demanding butyl substituent, is dimeric in the solid state.

’ EXPERIMENTAL PART General Methods. The starting compounds [2,6-(Me2NCH2)2C6H3](Ph)SnCl2,10 [2,6-(Me2NCH2)2C6H3](Bu)SnCl29c and Li2E12a were prepared according to the literature. Chalcogenes and Li[BHEt3] were 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, and operations with silver salts were light protected. The 1H, 13C, 77Se, 119Sn, and 125Te NMR spectra were recorded on a Bruker Avance 500 spectrometer at 300 K in C6D6 or CDCl3. The 1H, 13C, 77Se, 119Sn, and 125Te NMR chemical shifts δ are given in ppm and referenced to internal Me4Si (1H and 13C),

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external Me4Sn (119Sn), Me2Se (77Se, using Ξ value), and Me2Te (125Te, using Ξ value). Elemental analyses were performed on a LECO-CHNS-932 analyzer, but due to the high reactivity of compounds 4 and 5, we were not able to get sufficient analysis. The volatility measurements were performed using the static method with a STAT 6 apparatus.13a A detailed description of the apparatus and measuring methodology including the estimated uncertainties can be found in the literature.13b The heat capacities were obtained using the step method with a μDSC IIIa calorimeter (Setaram, France). The uncertainty of the heat capacity measurements is estimated to be less than 1%. A detailed description of the measuring procedure can be found in the literature.14 Synthesis of [{2,6-(Me2NCH2)2C6H3}(Ph)Sn(μ-S)]2 (2). A solution of 1 (0.15 g, 0.33 mmol) in THF (20 mL) was added dropwise to a solution of Li2S (0.11 g, 0.33 mmol of S) in THF (15 mL) at room temperature. The resulting mixture was stirred for a further 14 h at room temperature. After the solvent had been evaporated in vacuo the residue was suspended in CH2Cl2 (30 mL) and the resulting mixture was magnetically stirred for 10 min and then filtered. The solvent was evaporated in vacuo to leave a solid residue, which was washed with n-pentane to give 2 as a yellow powder (yield 0.1 g, 70%). For 2: mp 280283 °C. Anal. Calcd for C36H48N4S2Sn2 (838.32 g/mol): C, 51.58; H, 5.77. Found: C, 51.03; H, 5.65. 1H NMR (C6D6, 500.13 MHz): δ 2.15 (s, 12H, CH3), 2.79 (AX system, 2H, CH2, JAX = 23 Hz), 5.24 (AX system, 2H, CH2, JAX = 23 Hz), 6.917.32 (m, 6H, ArH), 8.16 (d, 2H, ArH, JHH = 11 Hz). 13 C NMR (C6D6, 125.77 MHz): δ 44.9 (CH3), 64.1 (CH2), 127.3 (C (3,5)), 127.7 (C0 (3,5)), 128.2 (C0 (4)), 128.4 (C(4)), 134.4 (C0 (2,6), 2 119 J( Sn, 13C) = 69 Hz), 143.4 (C0 (1), 1J(119Sn, 13C) = 456 Hz), 146.3 (C(2,6), 2J(119Sn, 13C) = 54 Hz), 149.3 (C(1), 1J(119Sn, 13C) not found). 119Sn NMR (C6D6, 186.49 MHz): δ 154.3. Synthesis of [2,6-(Me2NCH2)2C6H3](Ph)SndSe (3). A solution of 1 (0.15 g, 0.32 mmol) in THF (20 mL) was added dropwise to a suspension of Li2Se (0.25 g, 0.32 mmol of Se) in THF (15 mL) at room temperature. The resulting mixture was stirred for a further 24 h at room temperature. After the solvent had been evaporated in vacuo the residue was suspended in toluene (30 mL) and the resulting mixture was magnetically stirred for 10 min and then filtered. The solvent was evaporated in vacuo to leave a solid residue, which was washed with npentane to give 3 as a yellow powder (yield 0.1 g, 76%). For 3: mp 204205 °C. Anal. Calcd for C36H48N4Se2Sn2 (932.11 g/mol): C, 46.39; H, 5.19. Found: C, 46.02; H, 5.42. 1H NMR (CDCl3, 500.13 MHz): δ 2.03 (s, 6H, CH3), 2.58 (s, 6H, CH3), 3.62 (AB system, 2H, CH2), 3.83 (AB system, 2H, CH2), 7.197.39 (m, 6H, ArH), 7.67 (d, 2H, ArH, JHH = 8 Hz). 13C NMR (CDCl3, 125.77 MHz): δ 45.6 (CH3), 47.2 (CH3), 63.6 (CH2), 125.7 (C(3,5), 3J(119Sn, 13C) = 62 Hz), 128.6 (C0 (3,5), 3J(119Sn, 13C) = 58 Hz), 129.7 (C0 (4)), 130.4 (C(4)), 135.6 (C0 (2,6), 2J(119Sn, 13C) = 52 Hz), 140.5 (C0 (1), 1J(119Sn, 13C) = 658 Hz), 141.6 (C(1), 1J(119Sn, 13C) = 508 Hz), 143.6 (C(2,6), 2J(119Sn, 13 C) = 39 Hz). 77Se NMR (CDCl3): δ 570.9. 119Sn NMR (CDCl3, 186.49 MHz): δ 4.7 (1J(119Sn, 77Se) = 2965 Hz). Synthesis of [2,6-(Me2NCH2)2C6H3](Ph)SndTe (4). A solution of 1 (0.25 g, 0.55 mmol) in THF (20 mL) was added dropwise to a suspension of Li2Te (0.70 g, 0.55 mmol of Te) in THF (15 mL) at room temperature. The resulting mixture was stirred for a further 7 h at room temperature. After the solvent had been evaporated in vacuo the residue was suspended in toluene (30 mL) and the resulting mixture was magnetically stirred for 10 min and then filtered. The solvent was evaporated in vacuo to leave a solid residue, which was washed with npentane to give 4 as a yellow powder (yield 0.2 g, 81%). For 4: mp 191 °C with dec. 1H NMR (C6D6, 500.13 MHz): δ 1.63 (s, 6H, CH3), 2.30 (s, 6H, CH3), 2.91 (AB system, 2H, CH2), 3.20 (AB system, 2H, CH2), 6.797.12 (m, 6H, ArH), 7.70 (d, 2H, ArH, JHH = 8 Hz). 13C NMR (C6D6, 125.77 MHz): δ 44.3 (CH3), 47.7 (CH3), 62.7 (CH2), 125.4 (C(3,5), 3J(119Sn, 13C) = 55 Hz)), 128.3 (C0 (3,5), 3J(119Sn, 13C) = 51 Hz), 129.1 (C(4)), 129.7 (C0 (4)), 135.7 (C0 (2,6), 2J(119Sn, 13C) = 53 Hz), 5908

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Organometallics 142.8 (C0 (1), 1J(119Sn, 13C) = 402 Hz), 143.3 (C(1), 1J(119Sn, 13C) = 540 Hz)), 144.2 (C(2,6), 2J(119Sn, 13C) = 30 Hz). 119Sn NMR (C6D6, 186.49 MHz): δ 156.5 (1J(119Sn, 125Te) = 7574 Hz). 125Te NMR (C6D6): δ 1393.7. Synthesis of [2,6-(Me2NCH2)2C6H3](Bu)SndTe (5). A solution of [2,6-(Me2NCH2)2C6H3]BuSnCl2 (0.51 g, 0.12 mmol) in THF (20 mL) was added dropwise to a suspension of Li2Te (0.15 g, 0.12 mmol of Te) in THF (15 mL) at room temperature. The resulting mixture was stirred for a further 7 h at room temperature. After the solvent had been evaporated in vacuo the residue was suspended in toluene (30 mL) and the resulting mixture was magnetically stirred for 10 min and then filtered. The solvent was evaporated in vacuo to leave a solid residue that was washed with n-pentane to give 5 as a yellow powder (yield 0.4 g, 72%). For 5: mp 189 °C with dec. For monomeric stannanetellurone [L(Bu)SndTe]: 1H NMR (C6D6, 500.13 MHz): δ 1.05 (m, 3H, Bu), 1.20 (m, 2H, Bu), 1.56 (m, 2H, Bu), 1.77 (m, 2H, Bu), 1.85 (s, 6H, CH3), 2.32 (s, 6H, CH3), 2.87 (AB system, 2H, CH2), 3.30 (AB system, 2H, CH2), 6.78 (d, 2H, ArH), 7.01 (t, 1H, ArH). 13C NMR (C6D6, 125.77 MHz): δ 13.6 (C0 (1)), 19.4 (C0 (2)), 26.5 (C0 (3)), 29.3 (C0 (4)), 44.00 (CH3), 47.8 (CH3), 63.2 (CH2), 125.3 (C(3,5), 3J(119Sn, 13C) = 51 Hz), 129.1 (C(4)), 143.3 (C(2,6), 2J(119Sn, 13 C) = 11 Hz), 145.3 (C(1), 1J(119Sn, 13C) = 589 Hz). 119Sn NMR (C6D6, 186.49 MHz): δ 104.1 (1J(119Sn, 125Te) = 7389 Hz). For tellurido-bridged dimer [L(Bu)Sn(μ-Te)]2: 1H NMR (C6D6, 500.13 MHz): δ 0.91.7 (m, 9H, Bu), 2.19 (s, 12H, CH3), 2.64 (AX system, 2H, CH2, JAX = 12 Hz), 4.36 (AX system, 2H, CH2, JAX = 12 Hz), 7.007.16 (m, 6H, ArH). 119Sn NMR (C6D6, 186.49 MHz): δ 291.8 (1J(119Sn, 125Te) = 1472 Hz). Crystallography. Compound 2 was dissolved in CH2Cl2, and slow diffusion of a prepared solution gave X-ray quality material. Compounds 4 and 5 were dissolved in toluene (5 mL) and put into a freezer to crystallize at 40 °C, yielding material suitable for X-ray analysis. The X-ray data (Table 1) for colorless (1) and yellow crystals (4, 5) were obtained at 150 K using an Oxford Cryostream low-temperature 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 DENZO-SMN.15 The absorption was corrected by integration methods.16 Structures were solved by direct methods (Sir92)17 and refined by full matrix least-squares based on F2 (SHELXL97).18 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 Hiso(H) = 1.2Ueq(pivot atom) or of 1.5Ueq for the methyl moiety with CH = 0.96, 0.97, and 0.93 Å for methyl, methylene, and hydrogen atoms in aromatic rings, respectively. The crystal of 4 contains disordered toluene solvent molecules. Attempts were made to model this disorder or split it into two positions, but were unsuccessful. PLATON/SQUEZZE19 was used to correct the data for the presence of disordered solvent. A potential 3 was found; 118 electrons per unit cell worth of solvent volume of 401 Å scattering were located in the void. The calculated stoichiometry of solvent was calculated to be two molecules of toluene per unit cell, which results in 100 electrons per unit cell. Crystallographic data for structural analysis have been deposited with the Cambridge Crystallographic Data Centre, with CCDC nos. 835083, 835084, and 835085 for 5, 2, and 4, respectively. Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge CB2 1EY, UK (fax: +44-1223-336033; e-mail: [email protected] or www: http://www.ccdc.cam.ac.uk).

’ ASSOCIATED CONTENT

bS

Supporting Information. A possible transcis isomerization of dimeric diorganotin(IV) chalcogenides, concentration

ARTICLE

studies of compounds 2 and 3 in CDCl3 and C6D6, vapor pressures of 24, heat capacities of 2 and 3, and further details of the structure determination of compounds 2, 4, and 5, including atomic coordinates, anisotropic displacement parameters, and geometric data are available free of charge via the Internet at http://pubs.acs.org.

’ AUTHOR INFORMATION Corresponding Author

*E-mail: [email protected].

’ ACKNOWLEDGMENT 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 (project nos. VZ0021627501 and ME10049) for financial support. ’ REFERENCES (1) (a) Abramof, E.; Ferreira, S. O.; Rappl, P. H. O.; Closs, H.; Bandeira, I. N. J. Appl. Phys. 1997, 82, 2405. (b) Suzuki, N.; Adachi, S. Jpn. J. Appl. Phys. 1995, 34, 5977. (c) Singh, J. R.; Bedi, R. K. Thin Solid Films 1991, 199, 9. (d) Fukui, K. J. Phys. Soc. Jpn. 1992, 61, 2018. (e) Subba Rao, T.; Ray Samanata, B. K.; Chaudhuri, A. K. Thin Solid Films 1988, 165, 257. (2) (a) Chuprakov, I. S.; Dahmen, K. H.; Schneider, J. J.; Hagen J. Chem. Mater. 1998, 10, 3467. (b) Gou, X. L.; Chen, J.; Shen, P. W. Mater. Chem. Phys. 2005, 93, 557. (3) (a) The Chemistry of Metal CVD; Kodas, T., Hampden-Smith, M., Eds.; VCH: Weinheim, 1994; p 439 and references therein. (b) Pore, V.; Hatanp€a€a, T.; Ritala, M.; Leskel€a, M. J. Am. Chem. Soc. 2009, 131, 3478. (c) Bahr, S. R.; Boudjouk, P.; McCarthy, G. J. Chem. Mater. 1992, 4, 383. (d) Boudjouk, P.; Seidler, D. J.; Bahr, S. R.; McCarthy, G. J. Chem. Mater. 1994, 6, 2108. (e) Boudjouk, P.; Seidler, D. J.; Grier, D.; McCarthy, G. J. Chem. Mater. 1996, 8, 1189. (f) Cheng, Y. F.; Emge, T. J.; Brennan, J. G. Inorg. Chem. 1996, 35, 342. (g) Schneider, J. J.; Hagen, J.; Heinemann, O.; Bruckmann, J.; Kr€uger, C. Thin Solid Films 1997, 304, 144. (4) See for example: (a) Matsuhashi, Y.; Tokitoh, N.; Okazaki, R. Organometallics 1994, 13, 4387. (b) Seligson, A. L.; Arnold, J. J. Am. Chem. Soc. 1993, 115, 8214. (c) Schranz, I.; Grocholl, L.; Carrow, Ch.J.; Stahl, L.; Staples, R. J. J. Organomet. Chem. 2008, 693, 1081. (d) Puff, H.; Bertram, G.; Ebeling, B.; Franken, M.; Gattermayer; Hundt, R.; Schuh, W.; Zimmer, R. J. Organomet. Chem. 1989, 379, 235. (e) Hitchcock, P. B.; Jasim, H. A.; Lappert, M. F.; Leung, W.-P.; Rai, A. K.; Taylor, R. E. Polyhedron 1991, 10, 1203. (f) Weidenbruch, M.; Stilter, A.; Schlaefke, A.; Peters, K.; von Schnering, H. G. J. Organomet. Chem. 1995, 501, 67. (g) Sheldrick, W. S.; Wachhold, M. Angew. Chem. 1997, 109, 214. Angew. Chem., Int. Ed. Engl. 1997, 36, 206. (h) Tokitoh, N.; Saito, M.; Okazaki, R. J. Am. Chem. Soc. 1993, 115, 2065. (i) Matsuhashi, Y.; Tokitoh, N.; Okazaki, R.; Goto, M. Organometallics 1993, 12, 2573. (j) Puff, H.; Gattermayer, R.; Hundt, R.; Zimmer, R. Angew. Chem., Int. Ed. Engl. 1977, 16, 547. (k) Hitchcock, P. B.; Lappert, M. F.; Pierssens, L. J.-M.; Protchenko, A. V.; Uiterweerd, P. G. H. Dalton Trans. 2009, 4578. (5) For reviews, see: (a) Tokitoh, N.; Okazaki, R. Adv. Organomet. Chem. 2001, 47, 121. (b) Okazaki, R.; Tokitoh, N. Acc. Chem. Res. 2000, 33, 625. (c) Tokitoh, N.; Matsumoto, T.; Okazaki, R. Bull. Chem. Soc. Jpn. 1999, 72, 1665. (d) Escudie, J.; Ranaivonjatovo, H. Adv. Organomet. Chem. 1999, 44, 113. (e) Tokitoh, N.; Okazaki, R. In The Chemistry of Organic Silicon Compounds; Rappoport, Z., Apeloig, Y., Eds.; Wiley: New York, 1998; Vol. 2, p 1063. (f) Barrau, J.; Rima, G. Coord. Chem. Rev. 1998, 178180, 593. (g) Baines, K. M.; Stibbs, W. G. Adv. Organomet. Chem. 1996, 39, 275. For other example see: (h) Tokitoh, N.; Sadahiro, T.; Hatano, K.; Sasaki, T.; Takeda, N.; Okazaki, R. Chem. Lett. 2002, 31, 34. (i) Tokitoh, N.; Matsumoto, T.; Okazaki, R. J. Am. Chem. Soc. 5909

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