Reactivity of Organotin(I) Dimers RSnSnR (R = 2,6-(Me2NCH2)2C6H3

Article pubs.acs.org/Organometallics

Reactivity of Organotin(I) Dimers RSnSnR (R = 2,6-(Me2NCH2)2C6H3, 4‑t‑Bu-2,6-{P(O)(O‑i‑Pr)2}2C6H2) with Diaryl Dichalcogenides, ArEEAr (E = S, Se, Te; Ar = Ph, 2‑C5H4N): Control of Secondary Sn···Sn Interactions by Intramolecular Coordination and Identity of the Aryl Chalcogenate Michael Wagner,†,§ Christina Dietz,† Marek Bouška,‡,§ Libor Dostál,‡ Zdeňka Padĕlková,‡ Roman Jambor,*,‡ and Klaus Jurkschat*,† †

Lehrstuhl für Anorganische Chemie II, Technische Universität Dortmund, 44221 Dortmund, Germany Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Č s. legí 565, 53210 Pardubice, Czech Republic

‡

S Supporting Information *

ABSTRACT: The reactions of the in situ prepared organotin(I) compounds RSnSnR with diaryl dichalcogenides ArEEAr provided, depending on the ratio of the reactants, the intramolecularly coordinated heteroleptic organotin(II) chalcogenoarylates RSnEAr (1, R = 2,6-(Me2NCH2)2C6H3, E = S, Ar = Ph; 2, R = 2,6-(Me2NCH2)2C6H3, E = Se, Ar = Ph; 3, R = 2,6(Me2NCH2)2C6H3, E = Te, Ar = Ph; 6, R = 4-t-Bu-2,6-{P(O)(Oi-Pr)2}2C6H2, E = Se, Ar = Ph; 7, R = 4-t-Bu-2,6-{P(O)(O-iPr)2}2C6H2, E = Te, Ar = Ph; 8, R = 4-t-Bu-2,6-{P(O)(O-iPr)2}2C6H2, E = Se, Ar = 2-C5H4N) and the corresponding organotin(IV) compounds RSn(EAr) 3 (4, R = 2,6(Me2NCH2)2C6H3, E = S, Ar = Ph; 5, R = 2,6-(Me2NCH2)2C6H3, E = Se, Ar = Ph; 10, R = 4-t-Bu-2,6-{P(O)(O-i-Pr)2}2C6H2, E = S, Ar = 2-C5H4N), respectively. Compound 10 undergoes a thermally initiated cyclization reaction to give the benzoxaphosphastannole derivative {1(P),3(Sn)-Sn(S-Py)2-OP(O)(O-i-Pr)-6-t-Bu-4-P(O)(Oi-Pr)2}C6H2 (11). The compounds were characterized by 1H, 13C, 31P, 119Sn, and 125Te NMR and IR spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction analysis. The intramolecular Sn−N and Sn−O distances range between 2.501(3) (2) and 2.815(3) Å (4) and between 2.407(2) (8·C7H8) and 2.497(2) Å, respectively. Compounds 6 and 7 show intermolecular secondary Sn···Sn interactions at distances of 3.8876(3) and 3.8379(5) Å, respectively.

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(Me2NCH2)2C6H3M]n (M = Sb,12a Bi; n = 1−4) were shown to react with diphenyl dichalcogenides with oxidation.12b,c In previous papers we and others have shown that, in the solid state, intramolecularly coordinated low-valent organoelement compounds such as {2,4,6-(CF3)3C6H2}2Sn,13 4-t-Bu-2,6{P(O)(Oi-Pr)2}2C6H2SnX (X = Br, I),8d and 1-ClTe-8Me2NC10H614 exhibit secondary element···element interactions that are shorter than twice the van der Waals radius of the corresponding element. In the related compounds having a similar substituent pattern but lacking intramolecular coordination, such secondary interactions are absent.8d,14a On the basis of DFT calculations on the P-containing tin compound, this effect is traced to an interaction between the antibonding HOMO (lone electron pair at Sn) and the Sn−X σ* orbital, causing an energy decrease of the former and Sn···Sn binding.

INTRODUCTION The chemistry of tin(I) compounds that can formally be regarded as distannynes (or distannylenes), the tin analogues of alkynes, and their singly bonded isomers has attracted much attention in recent years.1 The reactivity of these types of compounds toward P4,2 H2,3 and olefins4 has been explored. Most remarkably the germanium species LGeGeL (L = N(Ar*)(SiMe3), Ar* = C6H2{C(H)Ph2}2Me-2,6,4) is oxidized by CO2 or CS2.5 The oxidation of an organodistannyne containing bulky substituents such as pyridine N-oxide was described by Power et al.6 In the course of our ongoing interest in intramolecularly coordinated low-valent organoelement compounds we synthesized a variety of N,C,N-7 and O,C,Ocoordinating8 pincer-type ligand-substituted compounds, including organotin(I) dimers of the type RSnSnR (R = 2,6(Me2NCH2)2C6H3,9 4-t-Bu-2,6-{P(O)(Oi-Pr)2}2C6H2)10), and studied their reactivity. 1 0 , 1 1 Recently, the related organoantimony(I) and organobismuth(I) compounds [2,6© 2013 American Chemical Society

Received: July 15, 2013 Published: August 20, 2013 4973

dx.doi.org/10.1021/om400694z | Organometallics 2013, 32, 4973−4984

Organometallics

Article

Scheme 1. Syntheses of Compounds 1−11

Figure 1. General view (SHELXTL) of 1 (molecule A) showing 30% probability displacement ellipsoids and the atom-numbering scheme. Hydrogen atoms are omitted for clarity. The view of molecule B is given in the Supporting Information.

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The availability of Sn−X σ* increases for X = I and by the P O→Sn coordination.8d Herein we report on the reactions of organotin(I) compounds RSnSnR (R = 4-t-Bu-2,6-{P(O)(Oi-Pr)2}2C6H2), 2,6-(Me2NCH2)2C6H3) with diaryl dichalcogenides ArEEAr (E = S, Se, Te; Ar = Ph, 2-C5H4NS) to give tin(II) and tin(IV) compounds, respectively.15 Also reported is the reaction of 4-tBu-2,6-{P(O)(Oi-Pr)2}2C6H2SnCl with PhSeSePh. We show that the reactivity of RSnSnR depends to some extent on the identity of R and E and, most importantly, that the degree of secondary Sn···Sn interactions in RSnEAr can also be controlled by both R and EAr.

RESULTS AND DISCUSSION

The reaction of the in situ generated distannylene derivatives RSnSnR (R = 2,6-(Me2NCH2)2C6H3,9 4-t-Bu-2,6-{P(O)(OiPr)2}2C6H210) with diaryl dichalcogenides gave, via redox-type reactions and depending on the reaction conditions and the stoichiometry, the corresponding organotin(II) (1−3, 6−8) or organotin(IV) compounds (4, 5) (Scheme 1). The compounds are colorless (1, 2, 4, 8) or yellow (3, 5−7) crystalline materials, which show good solubility in common aprotic organic solvents such as hexanes, toluene, and THF. Compound 3 is sensitive to moist air in solution and decomposes to give PhTeTePh and unidentified products. Compound 6 is sensitive toward hydrolysis. On contact to moist air the typical smell of selenophenol was detected. 4974


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The molecular structures of 1 (molecule A), 7, and 8 (as its toluene solvate 8·C 7 H 8 ), are shown in Figures 1−3,

Table 1. Selected Bond Lengths (Å) and Angles (deg) for 1 (Molecule A), 2 (Molecule A), and 4 Sn(1)−X(1) Sn(1)−X(2) Sn(1)−X(3) Sn(1)−C(1) Sn(1)−N(1) Sn(1)−N(2) C(1)−Sn(1)−N(1) C(1)−Sn(1)−N(2) N(2)−Sn(1)−N(1) C(1)−Sn(1)−X(1) C(1)−Sn(1)−X(2) C(1)−Sn(1)−X(3) N(1)−Sn(1)−X(1) N(1)−Sn(1)−X(2) N(1)−Sn(1)−X(3) N(2)−Sn(1)−X(1) N(2)−Sn(1)−X(2) N(2)−Sn(1)−X(3)

Figure 2. General view (SHELXTL) of 7 showing 30% probability displacement ellipsoids and the atom-numbering scheme.

1, X = S

2, X = Se

4, X = S

2.5080(8)

2.6322(4)

2.189(3) 2.620(3) 2.526(3) 71.20(10) 72.65(9) 143.80(7) 91.37(7)

2.189(3) 2.501(3) 2.579(3) 73.10(9) 72.02(9) 142.18(8) 83.92(7)

92.81(6)

94.51(6)

86.20(6)

95.92(6)

2.4691(10) 2.4146(9) 2.4721(10) 2.138(3) 2.760(3) 2.815(3) 69.52(11) 68.38(11) 110.08(9) 112.39(9) 125.70(9) 104.67(10) 76.53(7) 86.41(7) 167.39(7) 172.71(7) 76.39(7) 76.68(7)

= Te) > 8·C7H8 (85.45(6)°, E = S) > 2 (83.92(7)°, E = Se). They hint at high s character of the lone electron pair at the tin atoms. An even smaller angle of 78.60(3)° at the tin atom was found for Sn(SeArPri4)2 (ArPri4 = C6H3-2,6-(C6H3-2,6-i-Pr2)2).16 The values for the P-containing compounds 6, 7, 8·C7H8, and 4-t-Bu-2,6-{P(O)(O-i-Pr)2}2C6H2SnSPh8d fall in a narrower range than those of the N-containing compounds 1 and 2. The slightly smaller angle for the 2-C5H3NS-substituted derivative 8·C 7H8 in comparison to its thiophenolato-substituted analogue might be traced to the weak intramolecular (pyridine)N→Sn interaction at a N(32)−Sn(1) distance of 3.3030(24) Å, being shorter than the sum of the van der Waals radii of N and Sn (3.69 Å)17 but substantially longer than in the tin(IV) compound 2,6-(Me2NCH2)2C6H3SnMe2(SC4H3N-2) (3.118(11) Å).18 The intramolecular Me2N→Sn and O→Sn interactions at distances ranging between 2.501(3) (2) and 2.620(3) Å (1) and between 2.4069(17) (8·C7H8) and 2.4971(17) Å, respectively, are rather similar as compared with the corresponding distances in the parent halogenidosubstituted compounds 2,6-(Me2NCH2)2C6H3SnCl (2.525(8), 2.602(8) Å)19 and 4-t-Bu-2,6-{P(O)(O-i-Pr)2}2C6H2SnX (X = Cl, Br, I; 2.430(2)−2.473(2) Å),8d respectively, as well as in the thiophenolato-substituted derivative 4-t-Bu-2,6-{P(O)(O-iPr)2}2C6H2SnSPh (2.478(2) Å).8d The Sn(1)−Se(1) distances of 2.6322(4) (2) and 2.6373(3) Å (6) are slightly shorter than the Sn−Se distances in polymeric Sn(SePh)2 ranging from 2.6687(8) to 2.6832(7) Å.20 In 7, the Sn(1)−Te(1) distance of 2.8514(3) Å is slightly shorter than in polymeric Sn(TePh)2 (2.872(1)−2.895(1) Å)20 but longer than in (Me3P)Sn{TeSi(SiMe3)3}221 (2.834(1)/2.843(1) Å). The Sn(1)−Te(1)− C(31) angle is 94.33(6)°. A remarkable feature in the structures of the selenido- and telluridophenolates 6 and 7 in comparison to the corresponding thiophenolato-substituted derivatives 4-t-Bu-2,6-{P(O)(Oi-Pr)2}2C6H2SnSPh8d and 8·C7H8 are the secondary intermolecular Sn···Sn interactions at distances of 3.8876(3) Å (6, Figure 4) and 3.8379(5) Å (7, Figure S4 in the Supporting Information), being shorter than twice the van der Waals radius of the tin atom (4.34 Å).17

Figure 3. General view (SHELXTL) of 8·C7H8 showing 30% probability displacement ellipsoids and the atom-numbering scheme. Hydrogen atoms and disordered toluene solvate are omitted for clarity.

respectively, and those of 1 (molecule B), 2, and 6 are depicted in the Supporting Information (Figures S1−S3). Selected bond distances and angles are given in Tables 1 and 2. The unit cell of compound 1 contains two crystallographically independent molecules A and B, the geometric parameters of which are rather similar. Only those of molecule A are discussed. The tin atoms in the heteroleptic organotin(II) chalcogenoarylates 1, 2, 6, 7, and 8·C7H8 are each four-coordinated. The N(1)−Sn(1)−N(2) and O(1)−Sn(1)−O(2) angles are 143.80(7) (1), 142.18(8) (2), 152.13(5) (6), 151.92(5) (7), and 151.44(6)° (8·C7H8), respectively, deviating from 180°. The C(1)−Sn(1)−E(1) angles decrease in the order 1 (91.37(7)°, E = S) > 6 (89.56(5)°, E = Se) > 4-t-Bu-2,6{P(O)(O-i-Pr)2}2C6H2SnSPh (89.38(5)°)8d > 7 (88.74(8)°, E 4975


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Table 2. Selected Bond Lengths (Å) and Angles (deg) for 6, 7, 8·C7H8, and 9 Sn(1)−X Sn(1)−C(1) Sn(1)−O(1) Sn(1)−O(2) Sn(1)−N(32) C(31)−S(1) Sn(1)−Sn(1#) Sn(1)−Cl C(1)−Sn(1)−O(1) C(1)−Sn(1)−O(2) O(2)−Sn(1)−O(1) C(1)−Sn(1)−X O(1)−Sn(1)−X O(2)−Sn(1)−X C(30)−Se(1)−Sn(1) C(31)−S(1)−Sn(1) C(31)−Te(1)−Sn(1) Cl(1)−Sn(1)−Cl(2)

6, X = Se(1)

8·C7H8, X = S(1)

7, X = Te(1)

2.6373(3) 2.223(2) 2.4612(14) 2.4406(14)

2.5280(7) 2.240(3) 2.4069(17) 2.4971(17) 3.303(2) 1.764(3)

2.8514(3) 2.221(3) 2.437(2) 2.456(2)

3.8876(3)

9, X = Se(1) 2.5056(5) 2.141(4) 2.241(3) 2.235(3)

3.8379(5)

76.07(6) 76.14(6) 152.13(5) 89.56(5) 94.31(4) 87.56(4) 95.35(6)

76.29(8) 75.21(7) 151.44(6) 85.45(6) 86.52(4) 89.39(4)

2.4544(10)/2.5108(11) 79.86(13) 79.99(13) 159.84(9) 170.42(11) 100.74(7) 99.23(7)

76.09(10) 76.07(10) 151.92(7) 88.74(8) 89.77(5) 93.21(5)

102.20(9) 94.33(6) 179.20(5)

with compound 6, that a secondary Sn···Sn interaction is absent in the nitrogen donor containing organotin(II) selenophenolate 2. Apparently, not only the identity of the tin-bound substituent but also that of the intramolecular donor atom influences the degree of such interactions. Selected NMR data of compounds 1−11 are given in Table 3. The 119Sn NMR spectra reveal singlet resonances for compounds 1−3 and, as a result of coupling with the two phosphorus atoms, triplet resonances for 6−8. The chemical shifts for the latter compounds are shifted considerably to low frequency in comparison to those of 1−3, indicating the superior donor capacity of the phosphonyl moiety. In comparison to the parent thiophenolato-substituted compound 4-t-Bu-2,6-{P(O)(O-i-Pr) 2 } 2 C 6 H 2 SnSPh (δ( 119 Sn) −2, J(119Sn−31P) = 98 Hz)8d the pyridine thiolato substituted derivative 8 shows a marked low-frequency shift of δ −88 that might reflect a weak N→Sn interaction. However, one has to take into account as well that the thiopyridyl substituent itself has different group electronegativity than thiophenolate and this might also influence the chemical shift. The 119Sn NMR spectra of compounds 2, 3, 6, and 7 show 1J(119Sn−77Se) (1000, 985 Hz) and 1J(119Sn−125Te) (2102, 2117 Hz) couplings, respectively. These values are comparable to those found in the organotin(IV) selenides and tellurides with Sn−Se (range of 868−1300 Hz)23 and Sn−Te (range of 1624−3200 Hz) single bonds.24a−e,f The 1H NMR spectra of 1−3 showed broad resonances for the NCH3 protons and AX spin systems for the methylene NCH2 protons, whereas the spectra of compounds 6−8 each revealed four doublet resonances for the

Figure 4. Simplified view for the structure of compound 6 showing the secondary Sn···Sn interaction of 3.8876(3) Å. The t-Bu and i-Pr substituents and the Co, Cm, and Cp atoms of the phenyl groups are omitted for clarity.

The situation resembles that reported for the corresponding organotin(II) halides 4-t-Bu-2,6-{P(O)(O-i-Pr)2}2C6H2SnX (X = F, Cl, Br, I),8d,22 for which the representatives containing the heavier halogen substituents X = Br and X = I show such interactions at distances of 3.681(1) and 3.595(1) Å, respectively, whereas for the fluorido-22 and chloridosubstituted derivatives such interactions are absent.8d DFT calculations revealed this effect originates from an interaction between the antibonding HOMO (lone electron pair at Sn) and Sn−X σ* orbital that causes an energy decrease of the former and Sn···Sn binding. The availability of the Sn−X σ* orbital increases for X = I and by the PO→Sn coordination. In context with this it is even more surprising, in comparison

Table 3. Selected NMR Data (δ in ppm and J in Hz) for Compounds 1−11 1 δ(31P) δ(119Sn) δ(125Te) J(31P−117/119Sn) J(119Sn−31P) J(119Sn−77Se) J(119Sn−125Te) J(125Te−117/119Sn)

191

2 226

3 249

1000

4 −161

5

6

−273

35.2 45

1400

95/99 98 985

2102

7 34.3 97 240 96/100 101

8

9

10

35.4 −88.5

24.7 −588

23.1 −560

20.7/12.0 −503

11

89/94 94

79/82 83 2122

37 38

49 127/131 51 130

2117 2025/2118 4976


Organometallics

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The Sn(1) atom in 4 is [4 + 2]-coordinated by one carbon and three sulfur atoms, forming a distorted tetrahedron. The latter is capped by the N(1) and N(2) atoms approaching the Sn(1) atom via the tetrahedral faces defined by C(1), S(1), S(2), and C(1), S(2), S(3) at distances of 2.760(3) and 2.815(3) Å, respectively. These Sn−N bond distances indicate medium-strong Sn−N interactions, similarly to related N→ Sn(IV) intramolecularly coordinated compounds.7 The Sn−S distances in the range of 2.4030(11)−2.4725(11) Å are typical for Sn−S covalent single bonds.25 Both molecules A and B are propeller-type molecules with a clockwise (molecule A) and anticlockwise (molecule B, see the Supporting Information; Figure S5) orientation of the SPh substituents (when looking along the Sn(1)−C(1) and Sn(2)−C(31) axes, respectively; see the Supporting Information; Figure S6). They exist as pairs of enantiomers. The 119Sn NMR spectra of 4 and 5 showed single resonances at δ −161 (4) and −273 (5, 1J(119Sn−77Se) = 1400 Hz) that are shifted to low frequency in comparison with 1 and 2 as well as with nonsubstituted thio- and selenoorganotin(IV) derivatives, where Sn−N coordination is absent.26a The magnitude of the 1 119 J( Sn−77Se) coupling observed for 5 is comparable to those found in the related organotin(IV) selenides.23 The 1H NMR spectra showed broad signals at δ 3.51 (4) and 3.58 (5) for the NCH2 protons and singlet resonances at δ 2.09 (4) and 2.09 (5) for the CH3 protons. Notably, in contrast to the related compound 2, the organotin(II) derivative 6 does not react even under drastic conditions (THF, 120 °C, 2 h) with diphenyl diselenide to give the corresponding organotin(IV) product 4-t-Bu-2,6-{P(O)(Oi-Pr)2}2C6H2Sn(SePh)3. Thus, a 31P NMR spectrum of a solution of compound 2 in THF which had been heated to reflux overnight and then heated in a closed vessel to 120 °C for 2 h showed a main resonance at δ 34.9 (s, J(31P−117/119Sn) = 96/100 Hz, 2). However, the reaction of the organotin(II) chloride 4-t-Bu2,6-{P(O)(Oi-Pr)2}2C6H2SnCl with PhSeSePh gave, along with compound 6, the corresponding oxidation product 4-t-Bu-2,6{P(O)(Oi-Pr)2}2C6H2SnCl2(SePh) (9) as a yellow crystalline material that is readily soluble in organic solvents such as THF and benzene (Scheme 2). A 31P NMR spectrum of 9 shows a single resonance at δ 24.7 (J(31P−117/119Sn) = 79/82 Hz) while the 119Sn NMR spectrum exhibits a triplet resonance at δ −588 (J(119Sn−31P) = 83 Hz, 1 119 J( Sn− 77 Se) = 2122 Hz). Most remarkably, the 1 119 J( Sn−77Se) value is among the largest values ever reported for such a coupling and, to the best of our knowledge, is only topped by the 2274 Hz measured for [Sn4Se10]4−.26b The mechanism to account for the formation of compound 9 might be rather complex. One possibility is the following: 4-tBu-2,6-{P(O)(Oi-Pr)2}2C6H2SnCl oxidatively adds PhSeSePh to give 4-t-Bu-2,6-{P(O)(Oi-Pr)2}2C6H2SnCl(SePh)2 (I; Scheme 2) that was unambiguously identified in the reaction mixture by 31P (δ 24.44, J(31P−117/119Sn) = 43/45 Hz) and 119 Sn (δ −567, J(119Sn−31P) = 42 Hz, 1J(119Sn−77Se) = 1714 Hz) NMR spectroscopy. The observed satellite-to-signal-tosatellite integral ratio of 7.1:85:6.5 in the 119Sn NMR spectrum is close to that expected for I (7.6:84.8:7.6). We suggest that I reacts with 4-t-Bu-2,6-{P(O)(Oi-Pr)2}2C6H2SnCl to give 4-tBu-2,6-{P(O)(Oi-Pr)2}2C6H2SnSePh (6) and 9. The aforementioned reluctance of compound 6 to react with PhSeSePh is the reason for this reaction sequence. An alternative

OCH(CH3) and two complex patterns for the OCH(CH3) protons. These data indicate configurational stability of the tin atoms in compounds 1−3 and 6−8 on the 1H NMR time scale. A 13C NMR spectrum of 8 showed a resonance at δ 167.6 for the C2 carbon atom of the heteroaromatic, clearly indicating the preservation of the thiolate-bound isomer in solution.18 The signals for the heteroaromatic carbon atoms are broad as compared to those of the aromatic carbon atoms. This is possibly caused by some rotational freedom around the S− pyridine bond breaking the N→Sn interaction. The absence of thione vibrations in the IR spectrum of the solid corresponds to a thiolate-bound derivative in the solid state. As compounds 1−3 and 6−8 are rare examples of organotin(II) chalcogenoarylates, we were interested in whether the oxidation of the organotin(I) compounds RSnSnR could also provide the corresponding organotin(IV) chalcogenoarylates. Notably, related germanium(II) and germanium(IV) compounds have been reported.24g Thus, the treatment of [2,6-(Me2NCH2)2C6H3Sn]2 with an excess of the diaryl dichalcogenides PhEEPh (E = S, Se) yielded the corresponding organotin(IV) chalcogenoarylates 2,6-(Me2NCH2)2C6H3Sn(EPh)3 (4, E = S; 5, E = Se) (Scheme 1). In contrast, the reaction of [2,6-(Me2NCH2)2C6H3Sn]2 with PhTeTePh did not provide the tellurido−organotin(IV) derivative, but compound 3 was detected as the final product of the oxidation. Alternatively, compounds 4 and 5 were also obtained from the reactions of the corresponding organotin(II) chalcogenidophenolates 1 and 2, respectively, with Ph2E2 (E = S, Se) (Scheme 1). Compounds 4 and 5 were obtained as colorless crystalline materials that show good solubility in common aprotic organic solvents such as toluene and THF. Single crystals of 4 suitable for X-ray diffraction analysis were grown from a toluene solution at +4 °C. The unit cell contains two crystallographically independent molecules A and B, the geometric parameters of which differ only slightly. The structure of molecule A is shown in Figure 5. The structure of molecule B is given in the Supporting Information (Figure S5). Selected bond lengths and angles are shown in Table 1.

Figure 5. General view (SHELXTL) of 4 (molecule A) showing 30% probability displacement ellipsoids and the atom-numbering scheme. Hydrogen atoms are omitted for clarity. 4977


Organometallics

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Scheme 2. Synthesis of Compound 9

Figure 6. General view (SHELXTL) of 9 showing 30% probability displacement ellipsoids and the atom-numbering scheme. Hydrogen atoms are omitted for clarity.

23.1 (s, J(31P−117/119Sn) = 37 Hz) and δ −560 (t, J(119Sn−31P) = 38 Hz), respectively. Heating to reflux a solution of compound 10 in THF gave the benzoxaphosphastannole derivative {1(P),3(Sn)-Sn(S-Py)2OP(O)(O-i-Pr)-6-t-Bu-4-P(O)(Oi-Pr)2}C6H2 (11; Scheme 1) as a slightly yellow crystalline material that is readily soluble in THF and toluene. Such cyclization reactions, including mechanistic studies, have previously been reported for related organosilicon,28b,c -tin,28a,c,d -lead,28e and -bismuth28f derivatives. The molecular structure of compound 11, as its cyclohexane solvate 11·0.5C6H12, is shown in Figure 7. Selected bond lengths and angles are given in Table 4.

mechanism would involve reductive elimination of phenylselenium chloride, PhSeCl, from I to give 6, which in turn reacts with RSnCl under formation of 9. However, one argument against this mechanism is the observation that the addition of 1 molar equiv of PhSeCl to a solution of RSnCl gave a mixture consisting of 9 and RSnCl3. The latter does not appear in the reaction shown in Scheme 2. The addition of an excess of PhSeCl to the crude reaction mixture according to Scheme 2 gave exclusively RSnCl 3 (δ( 3 1 P) 22.7, J(31P−117/119Sn) = 268/280 Hz), which in turn proves that compound 6 is oxidized under these conditions while it is present in the crude reaction mixture according to Scheme 2. The molecular structure of compound 9 is shown in Figure 6, and selected bond distances and bond angles are given in Table 2. The Sn(1) atom in compound 9 is six-coordinated and shows a distorted-octahedral environment with the chlorine as well as the oxygen atoms being mutually trans. The distortion from the ideal geometry is expressed by the C(1)−Sn(1)− Se(1), Cl(1)−Sn(1)−Cl(2), and O(2)−Sn(1)−O(1) angles of 170.42(11), 179.20(5), and 159.84(9)°, respectively, deviating from 180°. The intramolecular Sn(1)−O(1) and Sn(1)−O(1) distances of 2.241(3) and 2.235(3) Å, respectively, are rather short and compare well with the distances found for the related organotin trichlorides 4-t-Bu-2,6-{P(O)(Oi-Pr)2}2C6H2SnCl3 (2.218(1), 2.221(1) Å) 2 7 and 4-t-Bu-2,6-{P(O)(OEt)2}2C6H2SnCl3 (2.225(3), 2.221(3) Å).28a The Sn(1)− Cl(1) (2.4544(10) Å) and Sn(1)−Cl(2) (2.5108(11) Å) distances are also close to and slightly longer, respectively, in comparison with the distances found for the latter compound (2.4345(8), 2.4410(8), 2.3379(7) Å;27 2.434(1), 2.422(1), 2.332(1) Å28a). The reaction of RSnSnR with 3 molar equiv of 2-pyridyl disulfide, (C5H4NS-2)2, provided the tin(IV) compound 10 (Scheme 1). It was not isolated, but its identity was confirmed by 31P and 119Sn NMR spectroscopy, showing resonances at δ

Figure 7. General view (SHELXTL) of 11·0.5C6H12 showing 30% probability displacement ellipsoids and the atom-numbering scheme. Hydrogen atoms and the solvate molecule are omitted for clarity. 4978


Organometallics

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Table 4. Selected Bond Lengths (Å) and Angles (deg) for 11·0.5C6H12 Sn(1)−O(1) Sn(1)−C(1) Sn(1)−N(31) Sn(1)−N(41) C(1)−Sn(1)−O(1) O(1)−Sn(1)−S(42) O(1)−Sn(1)−S(32)

2.1335(19) 2.155(3) 2.267(2) 2.281(3) 82.39(10) 94.83(6) 145.63(6)

Sn(1)−S(42) Sn(1)−S(32) Sn(1)−O(2) O(1)−Sn(1)−N(31) O(1)−Sn(1)−N(41)

81.02(8) 80.29(8)

characteristic of the high-temperature NMR spectrum is an onset coalescence of the heteroaromatic substituents manifested by the broadening and decline of the chemical shift difference. One possible mechanism to account for this stereochemical inversion at the tin atom could be of a “flipflop” type involving both Sn−N and Sn−S bond dissociation. In this context it is interesting to note that addition of 2mercaptopyridine to a solution of compound 11 caused in the 1 H NMR spectrum coalescence of the CH(CH3) resonance and broadening of all other resonances except those for t-Bu and H3Ar and H5Ar (Chart 1). The 13C NMR reveals the C-2 carbon atoms at δ 166.1 and 167.5, pointing to a high degree of thiolate character of the pyridyl sulfide substituents. The C-3 carbon atoms show unresolved 117/119Sn couplings of 56 and 59 Hz, respectively. The higher resistance toward hydrolysis of compound 11 in comparison to the tin(II) compounds is reflected in the ESIMS by observation of the [M + H]+ mass cluster at m/z 759.2. Additionally, mass clusters at m/z 1403.5 and 1537.6 assigned to dimeric species were also observed.

The tin atom in compound 11 is [6 + 1]-coordinated. The C(1), O(1), N(31), N(41), S(32), and S(42) atoms form a strongly distorted octahedron with C(1)−Sn(1)−N(41), N(31)−Sn(1)−S(42), and O(1)−Sn(1)−S(32) angles of 161.30(10), 147.55(7), and 145.63(6)°, respectively. The distortion from the ideal octahedral geometry originates from (i) the pincer-type ligand constraint, (ii) the strain imposed by the two four-membered SnSCN rings, and (iii) the O(2) atom approaching the Sn(1) atom via the octahedral face defined by C(1), S(32), S(42) at a distance of 2.843(2) Å. In contrast to the case for compound 7, the nitrogen atoms of both pyridyl ligands coordinate the tin atom at distances of 2.267(2) (Sn(1)−N(31))] and 2.281(3) Å (Sn(1)−N(41)), respectively. These values are comparable to that observed in SnCl2(C5H4NS)2 (2.259(2) Å).29 A 31P NMR spectrum of compound 11 exhibits two doublet resonances at δ 20.7 (J(31P−117/119Sn) = 49 Hz; P2) and 12.0 (J(31P−117/119Sn) = 127/131 Hz; P1) with resolved 117/119Sn satellites. The 119Sn NMR shows a doublet of doublets resonance at δ −503 (J(119Sn−31P) = 51 Hz, J(119Sn−31P) = 130 Hz). The 1H NMR shows three signals for the CH isopropyl protons and six doublet resonances for the CH3 protons. Additionally, two signal sets for the heteroaromatic part are observed which are less resolved than in the spectrum of compound 7. This reflects that the structure in solution is rather similar to the structure observed in the solid state. The H-6 protons closest to the nitrogen atoms show two distinct but unresolved 117/119Sn couplings of 27 and 33 Hz, respectively. This is not the case for compound 7. For the nonequivalent CH aryl protons 3Ar and 5Ar (Chart 1) unresolved 117/119Sn couplings of 33 and 50 Hz are observed.

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CONCLUSION The reactivity of [2,6-(Me2NCH2)2C6H3Sn]2 and [4-t-Bu-2,6{P(O)(O-i-Pr)2}2C6H2Sn]2 toward diorganodichalcogenides R2E2 was studied. The reactions provided rare examples of organotin(II)−thio, −seleno, and −tellurido derivatives (1−3, 6−8). The reactivity and structures in the solid state of these compounds depend on both the chalcogen atoms and the pincer-type ligand. Thus, the N,C,N-coordinated organotin(II) selenophenolate 2 can be easily oxidized by Ph2Se2 to give the organotin(IV) triselenophenolate 5, while the O,C,O-coordinated organotin(II) selenophenolate 6 does not react. Moreover, for the O,C,O-coordinated chalcogenolates 6 and 7 secondary tin−tin interactions were found. However, such interaction is absent in the corresponding N,C,N-coordinated derivative 2.

Chart 1. Numbering Scheme for the Assignment of NMR Signals for Compound 11a

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a

2.4907(9) 2.5016(9) 2.8425(19)

EXPERIMENTAL SECTION

General Considerations. All reactions were carried out under an atmosphere of dry argon in flame-dried glassware using Schlenk techniques. Solvents were purified by distillation from appropriate drying agents under argon. 4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl was synthesized as described and recrystallized from hexanes prior to use. 8 d 2,6(Me2NCH2)2C6H3SnCl and [2,6-(Me2NCH2)2C6H3Sn]2 were prepared according to literature procedures.9,19 Solutions of sodium naphthalenide in THF were freshly prepared. Bis(2-pyridinyl) disulfide was prepared according to a modified literature procedure with basic aqueous workup.30 NMR spectra were recorded on a Bruker AV DPX300/DRX 400/DRX 500 and Bruker Avance 500 or Varian Mercury instrument at room temperature unless otherwise stated. The assignment of the NMR signal was supported by 1H−1H gCOSY, 1 H−13C gHSQC/gHMBC, DEPT 135, and (in the case of 10) also by 1 H−31P gHMBC and 1H−119Sn gHMQC. NMR chemical shifts are

The N→Sn coordination is not shown for clarity.

The 2D-NOESY/ROESY spectra show cross peaks for the 3a/3b, 5a/5b, and 6a/6b protons (Chart 1) at the heteroaromatic substituents evidencing chemical exchange which, however, is slow on the 1H NMR time scale. 1H NMR at T = 354 K shows a broad unresolved signal for the CH3 protons. The signals of the Me2CH protons of the phosphonyl moiety (P2) are broadened, while that belonging to the P1 atom is still sharp. This is attributed to the rotation of the phosphonyl moiety about the C−P bond. A further 4979


Organometallics

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Synthesis of 2,6-(Me2NCH2)2C6H3Sn(SPh)3 (4). Method A: diphenyl disulfide (0.31 g, 1.44 mmol) and RSnSnR (0.30 g, 0.48 mmol) in nhexane (20 mL). Yield: 0.41 g, 67%. Method B: compound 1 (0.20 g, 0.47 mmol) and diphenyl disulfide (0.10 g, 0.47 mmol) in toluene (20 mL). Yield: 0.22 g, 73%. Mp: 214−218.5 °C. 1H NMR (C6D6, 500.18 MHz): δ 2.09 (s, 12H, NCH3), 3.51 (bs, 4H, CH2N), 6.76 (d, 3 1 J( H−1H) = 7.9 Hz, 2H, ArH), 6.88 (m, 9H, CHSPh), 7.00 (t, 3 1 J( H−1H) = 7.1 Hz, 1H, ArH), 7.45 (d, 3J(1H−1H) = 8.1 Hz, 6H, CHSPh). 13C{1H} NMR (C6D6, 125.77 MHz): δ 44.8 (NCH3), 63.5 (CH2N), 125.6 (C(3,5)), 128.3 (CSPh), 128.8 (CSPh), 129.7 (C(4), 4 13 J( C−119Sn) = 15 Hz), 133.1 (CSPh), 135.0 (CSPh), 142.5 (C(1), 1 13 J( C−119Sn) = 853 Hz), 145.7 (C(2,6), 2J(13C−119Sn) = 50 Hz). 119 Sn{1H} NMR (C6D6, 186.49 MHz): δ −161 (s). Anal. Calcd for C30H34N2S3Sn (637.5): C, 56.52; H, 5.38. Found: C, 56.5; H, 5.3. Synthesis of 2,6-(Me2NCH2)2C6H3Sn(SePh)3 (5). Method A: diphenyl diselenide (0.30 g, 0.96 mmol) and RSnSnR (0.20 g, 0.32 mmol) in n-hexane (20 mL). Yield: 0.39 g, 78%. Method B: compound 2 (0.80 g, 1.72 mmol) and diphenyl disulfide (0.53 g, 1.72 mmol) in toluene (20 mL). Yield: 1.09 g, 82%. Mp: 210 °C dec. 1H NMR (C6D6, 500.18 MHz): δ 2.09 (s, 12H, NCH3), 3.58 (bs, 4H, CH2N), 6.78 (d, 3J(1H−1H) = 8.1 Hz, 2H, ArH), 6.91 (m, 9H, CHSePh), 7.00 (t, 3J(1H−1H) = 7.0 Hz, 1H, ArH), 7.49 (d, 3J(1H−1H) = 7.5 Hz, 6H, CHSePh). 13C{1H} NMR (C6D6, 125.77 MHz): δ 45.5 (NCH3), 64.5 (CH2N), 127.0 (C(3,5)), 128.9 (CSePh), 129.2 (CSePh), 130.2 (C(4), 4J(13C−119Sn) = 17 Hz), 131.9 (CSePh), 137.5 (CSePh, 2 13 J( C−77Se) = 8.5 Hz), 142.2 (C(1), 1J(13C−119Sn) = 665 Hz), 146.8 (C(2,6), 2J(13C−119Sn) = 64 Hz). 119Sn{1H} NMR (C6D6, 186.49 MHz): δ −273 (s, 1J(119Sn−77Se) = 1400 Hz). Anal. Calcd for C30H34N2Se3Sn (778.2): C, 46.30; H, 4.40. Found: C, 46.3; H, 4.4. Synthesis of Compounds 6−8 and 10. To a solution of 4-t-Bu2,6-{P(O)(O-i-Pr)2}2C6H2SnCl (1−2.5 mmol) in THF (10 mL) was added a solution of sodium naphthalenide (1.06 equiv) in THF (10 mL) at −90 °C. The red solution was warmed to room temperature and stirred for 10 min to ensure complete conversion. The red solution was recooled to −90 °C, and the electrophile (0.5 equiv) was added. The solution was warmed to room temperature, during which time the red color disappeared, followed by stirring overnight. After the solvent had been removed in vacuo, the naphthalene was sublimed under high vacuum. The residue was extracted with toluene (20 mL) and filtered over Celite. The filtrate was concentrated, during which the crystallization of compound 6 was observed. Single crystals of 7 and 8·C7H8, respectively, were obtained by storing the corresponding solutions at −20 °C. The crystals were dried under high vacuum. 4-t-Bu-2,6-{P(O)(O-i-Pr)2}2C6H2SnSePh (6). With PhSeSePh (377 mg, 1.21 mmol), compound 6 was obtained as yellow crystals. Yield: 712 mg, 40%). Mp: 133 °C. 1H NMR (C6D6, 400.13 MHz): δ 0.93 (d, 3 1 J( H−1H) = 6.3 Hz, 6H, CH(CH3)2), 1.09 (d, 3J(1H−1H) = 6.0 Hz, 6H, CH(CH3)2), 1.11 (s, 9H, C(CH3)3), 1.15 (d, 3J(1H−1H) = 6.3 Hz, 6H, CH(CH3)2), 1.34 (d, 3J(1H−1H) = 6.0 Hz, 6H, CH(CH3)2), 4.42−4.53 (m, 2H, CH(CH3)2), 5.22−5.33 (m, 2H, CH(CH3)2), 7.00−7.04 (m, 1H, CHSePh), 7.08−7.13 (m, 2H, CHSePh), 8.00−8.04 (m, 2H, CHaryl), 8.25−8.27 (m, 2H, CHSePh). 13C{1H} NMR (C6D6, 100.63 MHz): δ 24.0−24.1 (m, CH(CH3)2), 24.2−24.3 (not resolved, CH(CH3)2), 24.6−24.7 (m, CH(CH3)2), 31.4 (s, C(CH3)3), 35.0 (s, C(CH3)3), 72.0−72.1 (m, CH(CH3)2), 72.7−72.8 (m, CH(CH3)2), 125.2 (s, CSePh), 129.1 (s, CSePh), 129.8 (s, CSePh), 132.2 (dd, 2 13 J( C−31P) = 16.0 Hz, 4J(13C−31P) = 4.4 Hz, C3/5aryl), 134.4 (dd, 1 13 J( C−31P) = 192 Hz, 3J(13C−31P) = 23.3 Hz, C2/6aryl), 136.2 (s, CSePh), 151.1 (t, 3J(13C−31P) = 12.6 Hz, C4aryl), 183.5 (t, 2J(13C−31P) = 35.0 Hz, C1aryl). 31P{1H} NMR (C6D6, 121.49 MHz): δ 35.2 (s, J(31P−117/119Sn) = 95/99 Hz, 1J(31P−13C) = 193 Hz, 2J(13C−31P) = 35.6 Hz). 119Sn{1H} NMR (C6D6, 111.92 MHz): δ 45 (t, J(119Sn−31P) = 98 Hz, 1J(119Sn−77Se) = 985 Hz). IR (KBr): ν̃ 3062 (Se−phenyl), 2978 (CH), 1575 (Se−phenyl), 1470 (Se−phenyl), 1190 (PO), 1143 cm−1 (PO). Anal. Calcd for C28H44SeO6P2Sn (736.3): C, 45.7; H, 6.0. Found: C, 45.5; H, 5.8. Reaction of 4-t-Bu-2,6-{P(O)(O-i-Pr)2}2C6H2SnSePh (6) with Ph2Se2. To a solution of 4-t-Bu-2,6{P(O)(O-i-Pr)2}2C6H2SnSePh

given in ppm and were referenced to Me4Si using the residual solvent signal (1H 7.16 ppm, 13C 128.39 ppm), H3PO4 (85%, 31P), Me4Sn (119Sn), or PhTeTePh (420 ppm, 125Te). Elemental analyses were performed on a LECO-CHNS-932 analyzer. Melting points are uncorrected and were measured on a Büchi M-560 and Stuart Melting point SMP3 instruments. IR spectra (cm−1) were measured on a Nicolet 5PC or Bruker IFS 28 device as KBr disks or as solids on a Perkin-Elmer Spectrum Two (ATR) instrument. The ESI-MS spectra were recorded at positive mode with a Thermoquest−Finnigan instrument using aqueous CH3CN as the mobile phase with a concentration of 0.1 mg/mL and a flow rate of 10 μL/min. The experimental isotopic pattern matched the theoretical patterns. Synthesis of Compounds 1−3. A hexane solution of the diphenyl dichalcogenide PhEEPh was added with stirring to a hexane solution of RSnSnR at −60 °C. The mixture was stirred for an additional 0.5 h at this temperature, and the reaction mixture was warmed to room temperature. The suspension was filtered, and the filtrate was concentrated to a volume of approximately 5 mL. The storage overnight at 5 °C gave colorless crystals suitable for X-ray analyses (1 and 2) and a yellow powder of 3, respectively. Synthesis of 2,6-(Me2NCH2)2C6H3SnSPh (1). Diphenyl disulfide (79 mg, 0.36 mmol) and RSnSnR (0.22 g, 0.36 mmol). Yield: 0.22 g, 72%. Mp: 107−110 °C. 1H NMR (C6D6, 500.18 MHz): δ 2.09 (br s, 12H, NCH3), 3.15 (AX system, 2J(1H−1H) = 12.1 Hz, 2H, CH2N), 3.58 (AX system, 2J(1H−1H) = 12.1 Hz, 2H, CH2N), 6.92 (d, 3J(1H−1H) = 8.1 Hz, 2H, ArH), 7.02 (t, 3J(1H−1H) = 7.9 Hz, 1H, ArH), 7.12 (m, 3H, CHSPh), 7.89 (d, 3J(1H−1H) = 5.5 Hz, 2H, CHSPh). 13C{1H} NMR (C6D6, 125.77 MHz): δ 45.6 (NCH3), 66.1 (CH2N), 123.8 (C(3,5)), 124.2 (CSPh), 127.7 (C(4)), 128.4 (CSPh), 133.3 (CSPh), 143.4 (C(2,6)), 146.8 (CSPh), 166.5 (C(1)). 119Sn{1H} NMR (C6D6, 186.49 MHz): δ 191 (s). Anal. Calcd for C18H24N2SSn (419.2): C, 51.58; H, 5.77. Found: C, 51.6; H, 5.8. Synthesis of 2,6-(Me2NCH2)2C6H3SnSePh (2). Diphenyl diselenide (0.48 g, 1.5 mmol) and RSnSnR (0.95 g, 1.5 mmol). Yield: 1.18 g, 83%. Mp: 94.2−96.8 °C. 1H NMR (C6D6, 500.18 MHz): δ 2.16 (br s, 12H, NCH3), 3.13 (AX system, 2J(1H−1H) = 13.2 Hz, 2H, CH2N), 3.61 (AX system, 2J(1H−1H) = 13.2 Hz, 2H, CH2), 6.91 (d, 3 1 J( H−1H) = 8.3 Hz, 2H, ArH), 7.11 (t, 3J(1H−1H) = 7.6 Hz, 1H, ArH), 7.13 (m, 3H, CHSePh), 8.05 (d, 3J(1H−1H) = 7.6 Hz, 2H, CHSePh). 13C{1H} NMR (C6D6, 125.77 MHz): δ 45.5 (NCH3), 65.9 (CH2N), 124.1 (C(3,5)), 124.4 (CSePh), 127.8 (C(4)), 128.4 (CSePh), 133.9 (CSePh), 135.2 (C(2,6)), 146.6 (CSePh), 166.0 (C(1)). 119Sn{1H} NMR (C6D6, 186.49 MHz): δ 226 (s, 1J(119Sn−77Se) = 1000 Hz). Anal. Calcd for C18H24N2SeSn (466.1): C, 46.39; H, 5.19. Found: C, 46.4; H, 5.2. Synthesis of 2,6-(Me2NCH2)2C6H3SnTePh (3). Diphenyl ditelluride (147 mg, 0.36 mmol) and RSnSnR (0.22 g, 0.36 mmol). Yield: 0.20 g, 54%. Mp: 115 °C dec. 1H NMR (C6D6, 500.18 MHz): δ 2.15 (br s, 12H, NCH3), 3.13 (AX system, 2J(1H−1H) = 12.2 Hz, 2H, CH2N), 3.61 (AX system, 2J(1H−1H) = 12.2 Hz, 2H, CH2N), 6.89 (d, 3 1 J( H−1H) = 8.1 Hz, 2H, ArH), 7.00 (t, 3J(1H−1H) = 7.9 Hz, 1H, ArH), 7.10 (m, 3H, CHTePh), 8.19 (d, 3J(1H−1H) = 8.1 Hz, 2H, CHTePh). 13C{1H} NMR (C6D6, 125.77 MHz): δ 45.1 (NCH3), 66.3 (CH2N), 109.8 (CTePh), 124.0 (C(3,5)), 126.0 (CTePh), 127.4 (C(4)), 128.4 (CTePh), 139.9 (C(2,6)), 146.5 (CTePh), 164.8 (C(1)). 119Sn{1H} NMR (C6D6, 186.49 MHz): δ 249 (s, 1J(119Sn−125Te) = 2102 Hz). Anal. Calcd for C18H24N2SnTe (514.7): C, 42.01; H, 4.70. Found: C, 42.1; H, 4.7. Synthesis of Compounds 4 and 5. Method A. A solution of the diphenyl dichalcogenide Ph2E2 (E = S, Se) in n-hexane was added with stirring to a solution of RSnSnR in n-hexane (20 mL) at room temperature. The mixture was stirred for 24 h to give a suspension containing a white precipitate. The latter was separated by filtration and recrystallized from toluene (5 mL) at −20 °C, affording colorless crystals of 4 and 5, respectively. Method B. Diphenyl disulfide, Ph2S2, and diphenyldiselenide, Ph2Se2, were added to toluene solutions of 1 and 2, respectively. The reaction mixtures were stirred at room temperature for 24 h. Each solution was concentrated to a volume of approximately 5 mL. Storage of the solutions at −20 °C afforded colorless crystals of 4 and 5. 4980


Organometallics

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45), 24.78 (s, J(31P−117/119Sn) = 44 Hz, RSn(SePh)2Cl (I), integral 22), 35.1 (s, J(31P−117/119Sn) = 96/100 Hz, RSnSePh (6), integral 13), 37.4 (s, J(31P−117/119Sn) = 120 Hz, RSnCl, integral 1). 119Sn{1H} NMR (C6D6, 111.92 MHz, −375 to −625 ppm): δ −587 (t, J(119Sn−31P) = 84 Hz, 1J(119Sn−77Se) = 2122 Hz, RSn(SePh)Cl2 (9), integral 74), −567 (t, J(119Sn−31P) = 42 Hz, 1J(119Sn−77Se) = 1711 Hz, RSn(SePh)2Cl (I), integral 26). (2) To 2,6-bis(diisopropoxyphosponyl)-4-tert-butylphenyltin chloride (458 mg, 0.74 mmol) in THF (2 mL) was added PhSeCl (148 mg, 0.77 mmol). The red-orange color of PhSeCl immediately disappeared, giving a deep yellow solution. From this solution a NMR spectrum was recorded. 31 1 P{ H} NMR (THF/C6D6, 121.49 MHz): δ 16.3 (s, RH, integral 16), 22.7 (s, J(31P−117/119Sn) = 268/280 Hz, RSnCl3, integral 21), 24.43 (s, J(31P−117/119Sn) = 86/90 Hz, RSn(SePh)Cl2 (9), integral 63). (3) In an NMR tube containing the crude reaction mixture from the reaction of RSnCl with Ph2Se2 was added PhSeCl until the red-orange color persisted. 31 1 P{ H} NMR (THF/C6D6, 121.49 MHz): δ 15.9 (s, RH, integral 17), 22.7 (s, J(31P−117/119Sn) = 268/280 Hz, RSnCl3, integral 83). 2,6-Bis(diisopropoxyphosponyl)-4-tert-butylphenyltin chloride (380 mg, 0.617 mmol) was stirred with Ph2Se2 (193 mg, 0.617 mmol) in THF (5 mL) overnight. From this solution, 31P and 119Sn NMR spectra were recorded. 31 1 P{ H} NMR (C6D6/THF, 121.49 MHz): δ 16.5 (s, RH, integral 12), 24.45 (s, J(31P−117/119Sn) = 85/89 Hz, RSn(SePh)Cl2 (9), integral 44), 24.49 (s, J(31P−117/119Sn) = 44 Hz, RSn(SePh)2Cl (I), integral 6), 34.8 (s, J(31P−117/119Sn) = 96/100 Hz, RSnSePh (6), integral 28), 37.1 (s, J(31P−117/119Sn) = 120 Hz, RSnCl, integral 9). 119 Sn{1H} NMR (C6D6/THF, 111.92 MHz, −250 to 250 ppm): δ 46 (t, J(119Sn−31P) = 101 Hz, RSnSePh (6)). The reaction mixture was filtered, and hexane was added. Compound 9 was isolated as yellow crystals, washed with toluene, and dried in vacuo. 4-tBu-2,6-{P(O)(OiPr)2}2C6H2Sn(SePh)Cl2 (92 mg, 18.5%) was obtained as a yellow powder. Mp: 150 °C dec. 1H NMR (C6D6, 400.13 MHz): δ 0.95−0.99 (overlapped, 21H, CH(CH3)2 + C(CH3)3), 1.28 (d, 3J(1H−1H) = 6.0 Hz, 12H, CH(CH3)2), 5.11−5.23 (m, 4H, CH(CH3)2), 7.05−7.12 (m, 3H, HSePh), 7.94 (pseudo-d, 3J(1H−31P) = 14.6 Hz, 2H, HAryl), 8.16−8.23 (m, 2H, H2,6SePh). 13C{1H} NMR (C6D6, 100.63 MHz): δ 23.6−23.9 (m, CH(CH3)2), 24.3−24.4 (m, CH(CH3)2), 31.3 (s, C(CH3)3), 35.4 (s, C(CH3)3), 75.1−75.2 (m, CH(CH3)2), 126.9 (dd, 1J(13C−31P) = 183 Hz, 3J(13C−31P) = 17.5 Hz, C2/6aryl), 128.2 (s, obscured by solvent, C4SePh), 128.7 (s, obscured by solvent, C3,5SePh), 131.1 (s, C1SePh), 131.6−131.8 (complex pattern, C3/5aryl), 139.4 (s, 3J(13C−117/119Sn) = 42 Hz, 2J(13C−77Se) = 8.3 Hz C2/6SePh), 153.8 (t, 3J(13C−31P) = 12.6 Hz, C4aryl), 175.2 (t, 2J(13C−31P) = 18.0 Hz, C1aryl). 31P{1H} NMR (C6D6, 121.49 MHz): δ 24.7 (s, J(31P−117/119Sn) = 79/82 Hz). 119 Sn{1H} NMR (C6D6, 111.92 MHz): δ −588 (t, J(119Sn−31P) = 83 Hz). 119Sn NMR (C6D6, 111.92 MHz): δ −588 (m). IR (ATR): ν̃ 562, 743, 865, 897, 992, 1130, 1152, 1171 (PO), 1378. Anal. Calcd for C28H44Cl2O6P2SeSn (807.2): C, 41.7; H, 5.5. Found: C, 41.6; H, 5.3. Synthesis of {1(P),3(Sn)-Sn(S-Py)2-OP(O)(O-i-Pr)-6-t-Bu-4-P(O)(Oi-Pr)2}C6H2 (11). With (Py-2-S)2 (561 mg, 2.54 mmol, 1.52 equiv) as described above to give a crude reaction mixture containing 10. 31 P{ 1 H} NMR (C 6 D 6 /THF, 81.02 MHz): δ 23.1 (s, J(31P−117/119Sn) = 37 Hz). 119Sn{1H} NMR (C6D6/THF, 111.92 MHz): δ −560 (t, J(119Sn−31P) = 38 Hz). After the solvent of the reaction mixture had been removed in vacuo, the residue was extracted with toluene/CH2Cl2 (20 mL). The volume of the extract was concentrated in vacuo, followed by addition of hexanes/THF. The resulting mixture was heated to reflux for 5 min. Compound 11 was crystallized at 7 °C as its cyclohexane solvate 11· 0.5C6H12. The solvate molecule was removed in vacuo at 50 °C. Yield: 701 mg, 56%. Mp: 145 °C dec. 1H NMR (C6D6, 400.13 MHz): δ 0.84 (d, 3J(1H−1H) = 6.3 Hz, 3H, CH(CH3)2), 1.04 (d, 3J(1H−1H) = 6.3 Hz, 3H, CH3 heterocycle), 1.08 (s, 9H, C(CH3)3), 1.21 (d, 3J(1H−1H) = 6.3 Hz, 6H, CH(CH3)2), 1.28 (d, 3J(1H−1H) = 6.3 Hz, 3H, CH3 heterocycle), 1.34 (d, 3J(1H−1H) = 6.3 Hz, 3H, CH(CH3)2), 4.28−

(621 mg, 1.358 mmol) in THF was added Ph2Se2 (424 mg, 1.358 mmol), and the mixture was heated to reflux overnight. A sample was taken from the crude reaction mixture, and NMR spectra were recorded. 31P{1H} NMR (C6D6/THF, 121.49 MHz): δ 34.9 (s, J(31P−117/119Sn) = 95/99 Hz, integral 80.3, 6), 24.1 (integral 1.0), 21.0 (integral 1.4), 16.5 (s, integral 12.2, RH), 14.9 (s, integral 4.0), 11.3 (integral 1.0). The remaining solution was heated for 2 h in a J. Young vessel at 120 °C, and a 31P NMR spectrum of the crude reaction mixture was recorded. 31P{1H} NMR (C6D6/THF, 81.02 MHz): δ 34.9 (s, J(31P−117/119Sn) = 96/100 Hz, integral 71.8, 6), 24.0 (m, integral 5.9), 16.5 (s, integral 11.1, RH), 14.9 (s, integral 4.5), 11.3 (m, integral 6.7). 4-t-Bu-2,6-{P(O)(O-i-Pr)2}2C6H2SnTePh (7). With PhTeTePh (361 mg, 0.88 mmol), compound 7 was obtained as yellow crystals. Yield: 621 mg, 45%. Mp: >65 °C dec. 1H NMR (C6D6, 300.13 MHz): δ 0.91 (d, 3J(1H−1H) = 5.9 Hz, 6H, CH(CH3)2), 1.09 (s, 9H, C(CH3)3), 1.12 (d, 3J(1H−1H) = 6.5 Hz, 6H, CH(CH3)2), 1.14 (d, 3J(1H−1H) = 6.5 Hz, 6H, CH(CH3)2), 1.33 (d, 3J(1H−1H) = 6.2 Hz, 6H, CH(CH3)2), 4.39−4.50 (m, 2H, CH(CH3)2), 5.18−5.29 (m, 2H, CH(CH3)2), 6.96−7.04 (m, 3H, CHTePh), 7.97−8.02 (m, 2H, CHaryl), 8.41−8.46 (m, 2H, CHTePh). 13C{1H} NMR (C6D6, 100.63 MHz): δ 24.0−24.1 (m, CH(CH3)2), 24.2−24.5 (not resolved, CH(CH3)2), 24.6−24.7 (m, CH(CH3)2), 31.4 (s, C(CH3)3), 35.0 (s, C(CH3)3), 72.0−72.1 (m, CH(CH3)2), 72.8−72.9 (m, CH(CH3)2), 110.1 (s, CipsoTePh), 126.5 (s, CTePh), 129.3 (s, J(13C−125Te) = 57.4 Hz, CTePh), 132.2 (dd, 2J(13C−31P) = 16.3 Hz, 4J(13C−31P) = 4.0 Hz, C3/5aryl), 134.4 (dd, 1J(13C−31P) = 193 Hz, 3J(13C−31P) = 23.6 Hz, C2/6aryl), 141.0 (s, J(13C−125Te) = 8.7 Hz, CTePh), 151.0 (t, 3J(13C−31P) = 12.7 Hz, C4aryl), 182.8 (t, 2J(13C−31P) = 34.9 Hz, C1aryl). 31P{1H} NMR (C6D6, 81.02 MHz): δ 34.3 (s, J(31P−117/119Sn) = 96/100 Hz); 119 Sn{1H} NMR (C6D6, 111.92 MHz): δ 97 (t, J(119Sn−31P) = 101 Hz, 1J(119Sn−125Te) = 2117 Hz). 125Te{1H} NMR (C6D6, 94.69 MHz): δ 240 (s, 1J(125Te−117/119Sn) = 2025/2118 Hz). IR (ATR, solid): ν̃ 1180 (PO), 1143 cm −1 (PO). Anal. Calcd for C28H44TeO6P2Sn (784.9): C, 42.85; H, 5.65. Found: C, 42.5; H, 5.75. 4-t-Bu-2,6-{P(O)(O-i-Pr)2}2C6H2Sn-2-SC4H3N (8). With (C4H3N-2S)2 (328 mg, 1.49 mmol), compound 8 was obtained as colorless crystals. The substance was recrystallized from hexanes/THF at −20 °C to get material of sufficient purity. Mp: 87 °C. 1H NMR (C6D6, 300.13 MHz): δ 0.94 (d, 3J(1H−1H) = 6.2 Hz, 6H, CH(CH3)2), 1.08 (d, 3J(1H−1H) = 5.9 Hz, 6H, CH(CH3)2), 1.12 (s, 9H, C(CH3)3), 1.16 (d, 3J(1H−1H) = 6.2 Hz, 6H, CH(CH3)2), 1.27 (d, 3J(1H−1H) = 6.2 Hz, 6H, CH(CH3)2), 4.42−4.57 (m, 2H, CH(CH3)2), 5.10−5.25 (m, 2H, CH(CH3)2), 6.44 (ddd, 4J(1H−1H) = 1.1 Hz, 3J(1H−1H) = 4.8 Hz, 3J(1H−1H) = 7.2 Hz, 1H, H-5), 6.90 (pseudo-td, 4J(1H−1H) = 1.9 Hz, 3J(1H−1H) = 8.0 Hz, 1H, H-4), 7.54 (d, 3J(1H−1H) = 8.0 Hz, 1H, H-3), 8.00−8.04 (m, 2H, CHaryl), 8.43 (ddd, 5J(1H−1H) = 1.1 Hz, 4 1 J( H−1H) = 1.8 Hz, 3J(1H−1H) = 4.8 Hz, 1H, H-6). 13C{1H} NMR (C6D6, 100.63 MHz): δ 24.1−24.7 (not resolved, CH(CH3)2), 31.4 (s, C(CH3)3), 35.0 (s, C(CH3)3), 71.7−72.0 (m, CH(CH3)2), 72.4−72.7 (m, CH(CH3)2), 117.8 (bs, C5Hetaryl), 126.6 (bs, C3Hetaryl), 132.0 (dd, 2 13 J( C−31P) = 16.5 Hz, 4J(13C−31P) = 3.9 Hz, C3/5aryl), 134.7 (dd, 1 13 J( C−31P) = 192 Hz, 3J(13C−31P) = 23.8 Hz, C2/6 aryl), 135.4 (bs, C4Hetaryl), 149.4 (bs, C6Hetaryl), 150.8 (t, 3J(13C−31P) = 12.6 Hz, C4aryl), 167.6 (bs, C2Hetaryl), 185.5 (t, 2J(13C−31P) = 36.0 Hz, C1aryl). 31P{1H} NMR (C6D6, 121.49 MHz): δ 35.4 (s, J(31P−117/119Sn) = 89/94 Hz, 1 31 J( P−13C) = 193 Hz). 119Sn{1H} NMR (C6D6, 111.92 MHz): δ −88.5 (t, J(119Sn−31P) = 94 Hz). IR (KBr): ν̃ 2977 (CH), 1568 (HetAr), 1548 (HetAr), 1443 (HetAr), 1410 (HetAr), 1194 (PO), 1178 (PO, shoulder), 1143 cm −1 (PO). Anal. Calcd for C27H43SNO6P2Sn (690.4): C, 47.0; H, 6.3; N, 2.0. Found: C, 47.15; H, 6.5; N, 1.95. 4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl(SePh)2 (9). NMR Experiments Regarding the Suggested Mechanism. (1) To 2,6bis(diisopropoxyphosponyl)-4-tert-butylphenyltin chloride (350 mg, 0.57 mmol) and Ph2Se2 (177 mg, 0.57 mmol) was added C6D6 (1 mL). NMR spectra of this solution were recorded immediately. 31 1 P{ H} NMR (C6D6, 121.49 MHz): δ 16.8 (s, RH, integral 19), 24.66 (s, J(31P−117/119Sn) = 85/89 Hz, RSn(SePh)Cl2 (9), integral 4981


Organometallics

Article

SHELXL9732 was applied to correct its thermal ellipsoids as well as C−C distances. In 8·C7H8 the toluene molecule is affected by disorder and refined with a split model over two positions (occupancy values 73:27). In compound 7 the tert-butyl group C(8)−C(10) and C(12) are affected by disorder; they were refined with a split model over two positions (occupancy values 55:45 and 75:25) and restrained to nearly isotropic behavior. In compound 9 the carbon atoms C(16) and C(25) are affected by disorder; they were refined with a split model over two positions (occupancy values 80:20 and 70:30). CCDC-927569 (1), CCDC-927568 (2), CCDC-927567 (4), CCDC-941590 (6), CCDC941592 (7), CCDC-941591 (8·C7H8), CCDC-945360 (9), and CCDC-941593 (11·0.5C6H12) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam. ac.uk/data_request/cif. The crystallographic data are given in the Supporting Information (Table S1). For decimal rounding of numerical parameters and su values the rules of IUCr have been employed.33 Figure 4 was prepared using Diamond 3.2i.34

4.39 (m, 1H, CH(CH3)2), 4.77−4.89 (m, 1H, CH heterocycle), 5.01− 5.12 (m, 1H, CH(CH3)2), 6.12 (pseudo-t, 3J(1H−1H) = 6.0 Hz, 1H, H5b), 6.34 (pseudo-t, 3J(1H−1H) = 6.0 Hz, 1H, H-5a), 6.62−6.69 (m, 2H, H-4a+b), 6.74 (d, 3J(1H−1H) = 8.0 Hz, 1H, H-3), 6.87 (d, 3 1 J( H−1H) = 8.0 Hz, H-3), 6.92 (d, 3J(1H−1H) = 5.0 Hz, J(1H−117/119Sn) = 34 Hz, 1H, H-6b), 8.02 (dd, 4J(1H−1H) = 1.6 Hz, 3J(1H−31P) = 13.4 Hz, 4J(1H−117/119Sn) = 50 Hz, 1H, CH5aryl), 8.48 (pseudo-d, 3J(1H−31P) = 12.6 Hz, 4J(1H−117/119Sn) = 33 Hz, 1H, CH3aryl), 9.45 (d, 3J(1H−1H) = 5.5 Hz, J(1H−117/119Sn) = 26.9 Hz, H6a). 13C{1H} NMR (C6D6, 100.63 MHz): δ 23.8 (d, 3J(13C−31P) = 5.8 Hz, CH(CH3)2), 24.4−24.6 (not resolved, CH(CH3)2), 24.8 (d, 3 13 J( C−31P) = 4.9 Hz, CH(CH3)2), 31.3 (s, C(CH3)3), 35.2 (s, C(CH3)3, 5J(13C−117/119Sn) = 8.8 Hz), 69.6 (d, 2J(13C−31P) = 6.8 Hz, CH(CH3)2), 71.3 (d, 2J(13C−31P) = 4.9 Hz, CH heterocycle), 71.7 (d, 2 13 J( C−31P) = 5.8 Hz, CH(CH3)2), 118.8 (s, C-5), 118.9 (s, C-5), 122.5 (s, 3J(13C−117/119Sn) = 56 Hz, C-3), 123.0 (s, 3J(13C−117/119Sn) = 59 Hz, C-3), 131.6 (dd, 2J(13C−31P) = 9.7 Hz, 4J(13C−31P) = 2.9 Hz, 3 13 J( C−117/119Sn) = 103 Hz, C3aryl), 132.0 (dd, 2J(13C−31P) = 11.7 Hz, 4 13 J( C−31P) = 2.9 Hz, 3J(13C−117/119Sn) = 82 Hz, C5aryl), 134.4 (dd, 1 13 J( C−31P) = 189 Hz, 3J(13C−31P) = 14.6 Hz, C6aryl), 139.6 (bs, C-4), 140.3 (bs, C-4), 143.0 (dd, 1J(13C−31P) = 169 Hz, 3J(13C−31P) = 15.0 Hz, C2aryl), 143.0 (bs, C-6b), 148.5 (bs, C-6a), 153.8 (pseudo-t, 3 13 J( C−31P) = 11.7 Hz, C4aryl), 158.1 (dd, 2J(13C−31P) = 14.1 Hz, 2 13 J( C−31P) = 19.0 Hz, C1aryl), 166.1 (s, C-2), 167.5 (s, C-2). 31P{1H} NMR (C6D6, 121.49 MHz): δ 20.7 (d, J(31P−31P) = 5.6 Hz, J(31P−117/119Sn) = 49 Hz, 1J(31P−13C) = 188 Hz, P2), 12.0 (d, J(31P−31P) = 6.7 Hz, J(31P−117/119Sn) = 131/127 Hz, 1J(31P−13C) = 167 Hz, P1). 119Sn{1H} NMR (C6D6, 111.92 MHz): δ −503 (dd, J(119Sn−31P) = 51 Hz, J(119Sn-−1P) = 130 Hz). 1H−1H NOESY/ ROESY cross peaks H6a+b; H5a+b; H3a+b. 1H NMR (toluene-d8, 500.13 MHz): δ 0.86 (d, 3J(1H−1H) = 6.1 Hz, 3H, CH(CH3)2), 1.03 (d, 3J(1H−1H) = 6.1 Hz, 3H, CH3 heterocycle), 1.12 (s, 9H, C(CH3)3), 1.21 (d, 3J(1H−1H) = 6.1 Hz, 6H, CH(CH3)2), 1.22 (d, 3 1 J( H−1H) = 6.1 Hz, 3H, CH3 heterocycle), 1.33 (d, 3J(1H−1H) = 6.1 Hz, 3H, CH(CH3)2), 4.31−4.37 (m, 1H, CH(CH3)2), 4.71−4.77 (m, 1H, CH heterocycle), 4.98−5.04 (m, 1H, CH(CH3)2), 6.11 (m, 1H, H-5b), 6.38 (pseudo-t, 3J(1H−1H) = 6.1 Hz, 1H, H-5a), 6.62−6.69 (m, 2H, H-4a+b), 6.72 (d, 3J(1H−1H) = 7.7 Hz, 1H, H-3), 6.85 (d, 3 1 J( H−1H) = 7.7 Hz, H-3), 6.91 (m, 1H, H-6b), 7.97 (pseudo-d, 3 1 J( H−31P) = 13.4 Hz, 4J(1H−117/119Sn) = 49 Hz, 1H, CH5aryl), 8.41 (pseudo-d, 3J(1H−31P) = 12.6 Hz, 4J(1H−117/119Sn) = 32 Hz, 1H, CH3aryl), 9.45 (d, 3J(1H−1H) = 4.2 Hz, H-6a). 1H NMR (toluene-d8, 500.13 MHz, 80.7 °C): δ 0.85−1.35 (not resolved, 27H, CH(CH3)2 + C(CH3)3), 4.40 (s, 1H, CH(CH3)2, ν1/2 50 Hz), 4.68−4.76 (m, 1H, CH heterocycle), 4.90 (s, 1H, CH(CH3)2, ν1/2 50 Hz), 6.21−6.37 (not resolved, 2H, H-5), 6.70−6.95 (not resolved, 5H, H-4 + H-3 + H-6b), 7.94 (pseudo-d, 3J(1H−31P) = 13.4 Hz, 4J(1H−117/119Sn) = 50 Hz, 1H, CH5aryl), 8.36 (pseudo-d, 3J(1H−31P) = 12.6 Hz, 4J(1H−117/119Sn) = 33 Hz, 1H, CH3aryl), 9.16 (s, H-6a, ν1/2 55 Hz). ESI-MS (+, CH3CN): m/ z 759.2 (M + H+)+, 781.1 (M + Na+)+, 1403.5 (2 M − SPy−)+, 1537.6 (2 M + Na+)+. IR (ATR, solid): ν̃ 1228 (PO, noncoordinating), 1167 (PO), 1140 cm−1 (PO). Anal. Calcd for C29H40S2N2O6P2Sn (757.4): C, 46.0; H, 5.3; N, 3.7. Found: C, 46.3; H, 5.55; N, 3.5. Crystallography. Intensity data for compounds 1, 2, and 4 were collected 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. Intensity data for compounds 6, 7, 8·C7H8, 9, and 11·0.5C6H12 were collected with an XcaliburS CCD diffractometer (Oxford Diffraction) using Mo Kα radiation at 110 K for all measurements. The structures of 1, 2, and 4 were solved with direct methods using SIR92,31 and the structures of 6, 7, 8·C7H8, 9, and 11·0.5C6H12 were solved with direct methods using SHELXS-97.32 Refinements were carried out against F2 by using SHELXL-97.32 All non-hydrogen atoms were refined using anisotropic displacement parameters, except the carbon atoms of the disordered toluene molecule in compound 8· C7H8. The C−H hydrogen atoms were positioned with idealized geometry and refined using a riding model. The carbon atoms C56− C60 in 4 are disordered, and treatment by an ISOR instruction from

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ASSOCIATED CONTENT

S Supporting Information *

CIF files and a table giving X-ray data for 1, 2, 4−9, and 11 and figures giving the molecular structures of 1 (molecule B), 2, 4 (molecule B), and 6, a view along the Sn−C axis (Diamond) of compound 4, an illustration of the secondary Sn···Sn interaction in compound 7, and 1H−31P gHMBC and 1 H−119Sn gHMQC NMR spectra of 11. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] (K.J.); roman. [email protected] (R.J.). Author Contributions §

This work contains part of the planned theses of M.W. and M.B. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS M.W. is grateful to the TU Dortmund for a scholarship. We thank Dr. Wolf Hiller for performing the VT 1H, 1H−31P gHMBC, and 1H−119Sn gHMQC NMR experiments on compound 11. This paper is dedicated to Professor HansLothar Keller on the occasion of his 70th birthday.

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REFERENCES

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Organometallics

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(34) Putz, H.; Brandenburg, K. Diamond-Crystal and Molecular Structure Visualization; Crystal Impact GbR, Kreuzherrenstr. 102, 53227 Bonn, Germany; http://www.crystalimpact.com/diamond.

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Reactivity of Organotin(I) Dimers RSnSnR (R = 2,6-(Me2NCH2)2C6H3

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