Crystal Structures of [Bu₂Sn(O₂PPh₂)₂], [Ph₂Sn(O₂PPh₂)₂], and [PhClSn(O₂PPh₂)OMe]₂. Raman Spectra of [Ph₂Sn(O₂PPh₂)₂] and [PhClSn(O₂PPh₂)OMe]₂

Abstract

n-Bu) 2 Sn(O 2 PPh 2 ) 2 ] (1), and [Ph 2 Sn(O 2 PPh 2 ) 2 ] (2) have been synthesized by the reactions of R 2 SnCl 2 (Rϭn-Bu, Ph) with HO 2 PPh 2 in Methanol. From the reaction of Ph 2 SnCl 2 with diphenylphosphinic acid a third product [PhClSn(O 2 PPh 2 )OMe] 2 (3) could be isolated. X-ray diffraction studies show 1 to crystallize in the monoclinic space group P2 1 /c with a ϭ 1303.7(1) pm, b ϭ 2286.9(2) pm, c ϭ 1063.1(1) pm, β ϭ 94.383(6)°, and Z ϭ 4. 2 crystallizes triclinic in the space group P1, the cell parameters being a ϭ 1293.2(2) pm, b ϭ 1478.5(4) pm, c ϭ 1507.2(3) pm, α ϭ 98.86(3)°, β ϭ 109.63(2)°, γ ϭ 114.88(2)°, and Z ϭ 2. Both com-

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

“…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. Furthermore, [Ph 2 Sb(μ‐O)(O 2 AsMe 2 )] 2 , which was prepared by treatment of (Ph 2 SbBrO) 2 with NaO 2 AsMe 2 in CH 2 Cl 2 shows a similar quadruply bridged structure with Sb 2 O 4 As 2 eight‐membered and Sb 2 O 2 four‐membered rings 9.…”

“…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.…”