tris[(trimethylphosphane)gold(I)]oxonium tetrafluoroborate | 155516-91-9

• 英文名称: tris[(trimethylphosphane)gold(I)]oxonium tetrafluoroborate
• 英文别名: tris[(trimethylphosphine)gold(I)]oxonium tetrafluoroborate；tris(trimethylphosphane)gold(I)oxonium tetrafluoroborate
• CAS: 155516-91-9
• 化学式: BF₄*C₉H₂₇Au₃OP₃
• 分子量: 921.938
• InChiKey: ISBYEWYMHVLUPK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  tris[(trimethylphosphane)gold(I)]oxonium tetrafluoroborate 在 NH₃ 作用下， 以 二氯甲烷 为溶剂， 以51%的产率得到μ4-nitrido-tetrakis[(trimethylphosphine)gold(I)] tetrafluoroborate
  参考文献：
  名称：

  Primary amines as nucleation centres for gold clustering, and the structural chemistry of polygold ammonium cations

  摘要：

  Treatment of tert-butylamine and benzylamine with [Au(PR'3)]BF4 led to the monoauration products [(R'3P)AuNH2R]+BF4- (R' = Me, R = Bu(t) 1a; R' = Me, R = CH2Ph 1b; R'3 = Ph2Me, R = Bu(t) 1c). The salts [{Au(PMe3)}3NR]+BF4- (R' = Me, R = Bu(t) 2a or CH2Ph 2b) derived from the same amines were obtained using the corresponding oxonium salt [{Au(PMe3)}3O]+BF4-. A diauration product [{Au(PMe3)}2NH(CH2Ph)]+BF4- 3 was generated upon slow hydrolytic degradation of 2b in solution. Treatment of NH(SiMe3)2 with [{Au(PMe3)}3O]+BF4- afforded both the tris- and tetra-aurated ammonium salts, [{Au(PMe3)}3NSiMe3]+BF4- 2c and [{Au(PMe3)}4N]+BF4- 4, depending on the reaction conditions. The cation of 2c is one of the very rare examples of silylammonium species. Compound 4 was also obtained from the oxonium salt and ammonia. All compounds have been characterized through analytical and spectroscopic data. The crystal structures of 1a, 1c and 3 have been determined by X-ray diffraction methods: 1c is a salt with monomeric gold ammonium cations, but 1a and 3 show supramolecular aggregation of the cations into dimers with short intercationic Au ... Au contacts.

  DOI：

  10.1039/dt9950000559

文献信息

• (Phosphine)gold(I) trifluoromethanesulfonates, trifluoroacetates and trichlorothioacetates †
  作者：Max Preisenberger、Annette Schier、Hubert Schmidbaur

  DOI：10.1039/a809714c

  日期：——

  [Tri(o-tolyl)phosphine]gold chloride was converted into the trifluoromethanesulfonate (triflate) in 95% yield by treatment with AgOS(O)2CF3 in tetrahydrofuran. The crystal structure determination of the CH2Cl2 solvate revealed non-ionic, molecular components [Au–O 2.110(3) Å, S–O–Au 120.4(2)°], which are associated into dimers via hydrogen bonds [O· · ·H–C 170.2°, C–H 0.969 Å, H· · ·O 2.575 Å] with two CH2Cl2

  （R 3 P）AuOC（O）CF 3类型的稳定的结晶（膦）金（I）三氟乙酸盐已由相应的氯配合物与AgOC（O）CF 3在四氢呋喃中的R = Me进行了高收率的制备， Ph或o- Tol。（Me 3 P）AuOC（O）CF 3的晶体结构具有三聚体，在角Au ··· Au ··· Au单元中具有两个短的亲金Au ··· Au触点。Trichlorothioacetic酸已经aurated使用[（R（高收率）3 P）的Au] 3 ö} + BF 4 -和的NaBF 4在二氯甲烷中得到同样稳定的化合物（R 3 P）AuSC（O）CCl 3，其中R = Me，Ph或邻-Tol。在这些产品中，三氯硫代乙酸酯基团仅硫键合到金原子上。甲基和邻甲苯基化合物是固态的二聚体，但缔合仅基于非常长的分子间Au ··· S和Au ····Cl分别接触。类似地制备了（三苯基膦）金硫代乙酸盐，但是该产物在固体和溶液状态
• Variations in the Chain Structure of Cationic (Phosphine)gold(I) Dialkyldithiophosphate Complexes
  作者：Max Preisenberger、Annette Schier、Hubert Schmidbaur

  DOI：10.1515/znb-1998-0801

  日期：1998.8.1

  appropriate quantities of tris[(phosphine)gold(I)]oxoniumtetrafluoroborates [(R′3P)Au]30}+ BF4- in dichloromethane gives di-or trinuclear complexes of the types (RO)2P[SAu(PR3)]2/3}+/2+ (2) BF4- as colour less, crystalline salts. As determined by single crystal X-ray diffraction studies, in the 1:2 complexes (with R = R′ = Me and R′ = Et, R = Ph and o-Tol), each gold atom is attached to a different

  摘要 用适量的三[(膦)金(I)]氧鎓四氟硼酸盐[(R'3P)Au]30}+ BF4-在二氯甲烷中处理二硫代磷酸二酯 (RO)2P(S)SH 得到二或三核(RO)2P[SAu(PR3)]2/3}+/2+ (2) - 类型的复合物为无色结晶盐。根据单晶 X 射线衍射研究确定，在 1:2 配合物（R = R' = Me 和 R' = Et，R = Ph 和 o-Tol）中，每个金原子连接到不同的硫原子，但具有短的阳离子内 Au-Au 接触。在第一种情况下（R = Et），这些阳离子通过分子间 Au-Au 接触形成串，但在第二种情况下通过额外的 Au-S 接触（R = Ph）。对于 R = o-Tol，由于空间位阻，阳离子根本不相关。该结果表明两种关联模式之间的能量差异非常小。1:3 配合物在溶液中是流动的，在 20°C 时的 NMR 光谱中显示出几乎等效的 R3PAU 基团，但在低温
• Gold(I) dimethyl- and diphenyl-dithiophosphinate complexes
  作者：Max Preisenberger、Andreas Bauer、Annette Schier、Hubert Schmidbaur

  DOI：10.1039/a706033e

  日期：——

  In an attempt to carry out polyauration of dithiophosphinate units, diphenyldithiophosphinic acid, Ph2P(S)SH, was treated with the reagents [(R′3P)Au]3O}+BF4– to give compounds Ph2P[SAu(PR′3)]2}+BF4– with R′ = Ph, Me or o-tolyl (o-Tol) (1–3). The symmetrical Au· · ·Au bonded structure of complex 1 was confirmed by a single-crystal X-ray diffraction study. Intercationic contacts are found only between gold and sulfur atoms. The analogous reaction with PhP(S)(SSiMe3)2 gave an unstable product of the composition PhP[SAu(PPh3)]3}+BF4–4, for which a solution structure with mirror-symmetry is proposed on the basis of low-temperature NMR data. Attempts to polyaurate dimethyldithiophosphinic acid led to cleavage of the P–S bonds with formation of known trigold sulfonium salts. (Phosphine)gold(I) dithiophosphinates Me2P(S)SAu(PR′3) were obtained from Me2P(S)SNa and chloro(phosphine)gold complexes (R′ = Me, Ph or o-Tol, 5–7 respectively). The crystal and molecular structure of compound 5 was determined. In the crystal, the compound forms two crystallographically independent, centrosymmetrical dimers with Au· · ·Au contacts [3.1152(5) and 3.1466(5) Å] between ‘crossed’ monomers. With (Me2S)AuCl as a precursor, the product of the reaction with Me2P(S)SNa was [Me2P(S)SAu]28. Compound 8 is a dinuclear complex with an elongated eight-membered ring structure in a chair conformation. The crystal-structure analysis reveals the expected transannular Au· · ·Au contacts [3.1949(9) Å], but no intermolecular contacts are discernible.

  为了尝试对二硫代膦酸单元进行聚芳香化，二苯基二硫代膦酸 Ph2P(S)SH 与试剂 [(R′3P)Au]3O}+BF4- 进行了处理，得到了化合物 Ph2P[SAu(PR′3)]2}+ - ，其中 R′ = Ph、Me 或邻甲苯基 (o-Tol) (1-3)。单晶 X 射线衍射研究证实了复合物 1 的对称金-金键结构。仅在金原子和硫原子之间发现了互成接触。与 PhP(S)(SSiMe3)2 的类似反应产生了一种成分为 PhP[SAu(PPh3)]3}+ -4的不稳定产物，根据低温核磁共振数据提出了具有镜像对称性的溶液结构。对二甲基二硫代磷酸进行聚牛磺酸化的尝试导致了 P-S 键的裂解，并形成了已知的三金锍盐。(从 Me2P(S)SNa 和氯（膦）金络合物（R′= Me、Ph 或 o-Tol，5-7）中得到了（膦）金（I）二硫代磷酸盐 Me2P(S)SAu(PR′3)。化合物 5 的晶体和分子结构已经确定。在晶体中，该化合物形成两个晶体学上独立的、中心对称的二聚体，"交叉 "单体之间有 Au- - -Au 接触 [3.1152(5) Å 和 3.1466(5) Å]。以 (Me2S)AuCl 为前体，与 Me2P(S)SNa 反应的产物为 [Me2P(S)SAu]28。化合物 8 是一种双核复合物，具有椅状构象的拉长八元环结构。晶体结构分析显示了预期的跨annular Au- - Au 接触 [3.1949(9) Å]，但没有发现分子间接触。
• Gold clustering at the methylthiolate anion
  作者：Alexander Sladek、Kluas Angermaier、Hubert Schmidbaur

  DOI：10.1039/cc9960001959

  日期：——

  By reaction with the aurating agents [Au(PMe3)]BF4/O3SCF3 or [(Me3P)Au}3O]BF4 in molar ratios 1 : 1, 1 : 2 or 1 : 3, sodium methylthiolate NaSMe is converted into dinuclear [Au(PMe3)(SMe)]2 1, tetranuclear [MeS[Au(PMe3)]2}2X2](X = BF4 2a, O3SCF3 2b) and the novel trinuclear [MeSAu(PMe3)}3][O3SCF3]2 3 complexes.

  通过与极化剂 [Au(PMe3)] /O3SCF3 或 [(Me3P)Au}3O] 以摩尔比 1 : 1、1 : 2 或 1 ：甲硫醇钠 NaSMe 被转化为双核 [Au(PMe3)(SMe)]2 1、四核 [MeS[Au(PMe3)]2}2X2]（X = BF4 2a，O3SCF3 2b）和新型三核 [MeSAu(PMe3)}3][O3SCF3]2 3 复合物。
• Further Gold Aggregation at a Pentanuclear Gold Cluster with Hypercoordinate Interstitial Nitrogen
  作者：Klaus Angermaier、Hubert Schmidbaur

  DOI：10.1021/ic00115a050

  日期：1995.5

  Reaction of hexamethyldisilazane with chloro(trimethylphosphine)gold(I) and tris-[(trimethylphosphine)gold(I)]oxonium tetrafluoroborate gives a heptanuclear gold complex in which a dicationic, nitrogen-centered, trigonal-bipyramidal gold cluster is associated with 2 equiv of Me(3)PAuCl through short Au-Au contacts to the equatorial gold atoms.[GRAPHICS]ped by a Cp '' Co unit and a [(Cp '' Co)(2) mu-CO)] dimer coordinates to only three P atoms from below, resulting in a kite-like distortion of the P-4 molecule with two short and two long P-P distances. The longer distances could be considered to be on the borderline between a bonding P-P length and the van der Waals contact. The factors controlling the structure have been studied by EHT calculations.