Crystal Structures and Spectral Studies of [Ph₃Sn(O₂AsMe₂)], [Bu₂ClSn(O₂AsMe₂)] and [PhClSn(O₂AsMe₂)(μ‐OMe)]₂

Abstract

[Ph3Sn(O2AsMe2)] (1) and [PhClSn(O2AsMe2)(μ‐OMe)]2 (3) have been synthesized by treatment of Ph3SnCl and Ph2SnCl2 with Na(O2AsMe2) in methanol, respectively. [Bu2ClSn(O2AsMe2)] (2) has been prepared by the reaction of Bu2SnCl2 with HO2AsMe2 in methanol. X‐ray diffraction studies show 1 to crystallize in the monoclinic space group P21/n with a = 699.8(1), b = 1961.4(2), c = 1433.6(2) pm, β = 95.17(1)°, and Z = 4. 2 also crystallizes monoclinic in the space group P21/m, the cell parameters being a = 480.6(1), b = 1992.7(2), c = 808.8(1) pm, β = 103.726(5)°, and Z = 2. Both compounds form infinite chains with alternating (Me2AsO2)− and (R3Sn)+ or (R2ClSn)+ units. The dimer 3 consists of 8‐membered (OSnOAs)2 rings in which the tin atoms are bridged by methanolate bridges. It crystallizes triclinic in the space group $\rm P{\bar 1}$ with a = 822.8(2), b = 910.4(2), c = 929.2(2) pm, α = 77.04(3)°, β = 82.35(3)°, γ = 68.69(3)°, and Z = 1 for the dimer. The vibrational and mass spectra of 1, 2 and 3 are given and discussed.

Synthesis, Spectroscopic Studies and Crystal Structures of [Et2Sn(O2AsMe2)2] and [Ph2Sn(O2AsMe2)(μ‐OMe)]2

“…The reactions of Ph 2 SnCl 2 with NaO 2 AsMe 2 and with HO 2 PPh 2 in methanol produce also dimers containingMeO groups [PhClSn(O 2 AsMe 2 )(μ‐OMe)] 2 and [PhClSn(O 2 PMe 2 )(μ‐OMe)] 2 , which indicate that methanol behaves as solvent and reactant. X‐ray diffraction studies show that 2 and [PhClSn(O 2 AsMe 2 )(μ‐OMe)] 2 2 are centrosymmetric dimers involving hexacoordinate tin atoms connected by two bridges of O 2 AsMe 2 and two bridges of OMe groups forming Sn 2 O 4 As 2 eight‐membered and Sn 2 O 2 four‐membered rings. A similar structure has been found for the analogous phosphorus‐containing dimer [PhClSn(O 2 PMe 2 )(μ‐OMe)] 2 8.…”

“…Compound 2 forms a centrosymmetric dimer consisting of (Sn–O–As–O) 2 eight‐membered rings, in which the tin atoms are linked by two MeO − bridges (Figure 2). An analogue configuration has been found for an arsinate2 and a phosphinate,8 in which the tin atoms are asymmetrically substituted by a chloride and a phenyl group causing the bridge to be strongly asymmetric on account of the different trans ‐positioned ligands. Bond lengths and bond angles (Table 5) correspond well with the values found in the above arsenate,2 except for the angles O–As–O and Sn–O–Sn in the almost symmetrical MeO − bridge, which are by 3° wider.…”

“…An analogue configuration has been found for an arsinate2 and a phosphinate,8 in which the tin atoms are asymmetrically substituted by a chloride and a phenyl group causing the bridge to be strongly asymmetric on account of the different trans ‐positioned ligands. Bond lengths and bond angles (Table 5) correspond well with the values found in the above arsenate,2 except for the angles O–As–O and Sn–O–Sn in the almost symmetrical MeO − bridge, which are by 3° wider. This is in accordance with the greater Sn–Sn distance in 2 (347.97(2) pm as compared to 340.84(2) pm in the phenyl‐chloro‐substituted compound) and is due to the steric needs of the two phenyl groups.…”

“…The reactions of diorganotin dichlorides R 2 SnCl 2 with HO 2 AsMe 2 in methanol at ambient temperature produce [ R 2 ClSn(O 2 AsMe 2 )] ( R 2 = Me 2 , Et 2 ,1 Bu 2 2). Meanwhile [Ph 3 Sn(O 2 AsMe 2 )] and the dimer [PhClSn(O 2 AsMe 2 )(μ‐OMe)] 2 were formed by the reaction of NaO 2 AsMe 2 with Ph 3 SnCl and Ph 2 SnCl 2 respectively 2. Crystalline [Bu 2 Sn(O 2 AsMe 2 ) 2 ] was synthesized by the reaction of Bu 2 SnO and HO 2 AsMe 2 3.…”

“…Crystalline [Bu 2 Sn(O 2 AsMe 2 ) 2 ] was synthesized by the reaction of Bu 2 SnO and HO 2 AsMe 2 3. X‐ray diffraction studies of [ R 2 ClSn(O 2 AsMe 2 )] and [Ph 3 Sn(O 2 AsMe 2 )] show that the O 2 AsMe 2 groups behave as bidentate bridging ligands between the tin atoms, thus forming polymeric chain structures 1,2. A two‐dimensional polymeric structure with (SnOAsO) 4 sixteen‐membered rings was reported for [Bu 2 Sn(O 2 AsMe 2 ) 2 ] 3…”