Abstract

The product of the reaction between tetraphenylbismuth chloride Ph₄BiCl (I) synthesized via the dephenylation of pentaphenylbismuth with hydrochloric acid and potassium hexabromoplatinate (2 : 1 mol/mol) in water after recrystallization from dimethylsulfoxide is О-dimethylsulfoxydotetraphenylbismuth S-dimethylsulfoxidotribromoplatinate [Ph₄BiDMSO-O][PtBr₃DMSO-S] (II). Recrystallization of the complex synthesized from compound I and potassium hexachloroplatinate from acetonitrile gives tetraphenylbismuth hexachloroplatinate [Ph₄Bi]₂[PtCl₆] (III). Structures I–III have been studied by X-ray diffraction. The coordination polyhedron of bismuth atoms in compounds I and II (a crystal contains two types of crystallographically independent ions) is a distorted trigonal bipyramid with heteroatoms in axial positions, and the CBiCl and CBiО axial angles are 175.8(1)°, 177.4(3)°, and 177.3(4)°, respectively; the Bi–Cl distances are 2.912(2) Å (I), and Bi–О is 2.78(1) and 2.76(1) Å (II); in the equatorial plane, the Bi–C bonds and the CBiC angles are, respectively, 2.204(4)–2.224(4) Å and 113.42(16)°–123.35(15)° in I, 2.170(13)–2.181(12) Å, 2.155(12)–2.187(13) Å and 110.9(4)°–123.8(4)°, 111.0(4)°–123.3(5)° in II. The cation in structure III is a distorted tetrahedron, Bi–C bonds vary within a range of 2.199(4)–2.231(4) Å, and the CBiC angles are 102.6(2)°–126.5(2)°. The platinum atoms in the anions of compound II are tetracoordinated, the trans-BrPtBr and trans-SPtBr angles are ranged within 176.51(11)°–177.62(6)°; the Pt–Br bonds are 2.402(3)–2.424(3) Å, and the Pt–S distances are 2.200(4) and 2.182(4) Å. In the centrosymmetric octahedral anions of compound III, the trans-ClPtCl angles are 180°, and the cis-ClPtCl angles are 88.71(6)°–91.29(6)°; the Pt–Cl bonds are 2.329(2)–2.3350(18) Å.

中文翻译：

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四苯基铋（V）衍生物Ph 4 BiCl，[Ph 4 BiDMSO-O] [PtBr 3 DMSO- S]和[Ph 4 Bi] 2 [PtCl 6]：合成与结构

摘要

之间的反应的产物tetraphenylbismuth氯化物博士₄ BiCl（我）通过用盐酸和钾hexabromoplatinate pentaphenylbismuth的dephenylation合成（2:1摩尔/摩尔）在二甲亚砜从再结晶后的水是О -dimethylsulfoxydotetraphenylbismuth小号-dimethylsulfoxidotribromoplatinate [PH ₄ BiDMSO- O ] [PtBr ₃ DMSO- S ]（II）。由化合物I和六氯铂酸钾由乙腈合成的配合物重结晶，得到四氯六铂铂酸铋[Ph ₄ Bi]₂ [PtCl ₆ ]（III）。通过X射线衍射研究了结构I – III。化合物I和II中的铋原子配位多面体（晶体包含两种晶体学上独立的离子）是在轴向位置带有杂原子的扭曲三角双锥体，CBiCl和CBiО轴向角为175.8（1）°，177.4（3） ）°和177.3（4）°；Bi–Cl距离为2.912（2）Å（I），Bi–О距离为2.78（1）和2.76（1）Å（II）；在赤道平面，碧-C键和CBIC角度分别是2.204（4）-2.224（4）和113.42（16）°-123.35（15）°在我，2.170（13）-2.181（12）埃，2.155（12）-2.187（13）a和110.9（4）°-123.8（4）°，111.0（4）°-123.3（5）°的II。结构III中的阳离子是扭曲的四面体，Bi–C键在2.199（4）–2.231（4）Å的范围内变化，并且CBiC角为102.6（2）°–126.5（2）°。化合物II的阴离子中的铂原子是四配位的，反式-BrPtBr和反式-SPtBr的角度范围为176.51（11）°-177.62（6）°；Pt–Br键为2.402（3）–2.424（3）Å，Pt–S距离为2.200（4）和2.182（4）Å。在化合物III的中心对称八面体阴离子中，反式-ClPtCl角为180°，顺式为-ClPtCl角为88.71（6）°–91.29（6）°；Pt–Cl键为2.329（2）–2.3350（18）Å。