Chandrasekaran P, Mague Joel T, Balakrishna Maravanji S
Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology-Bombay, Mumbai, 400076, India.
Dalton Trans. 2009 Jul 28(28):5478-86. doi: 10.1039/b903075a. Epub 2009 May 28.
Reactions of two equivalents of [AuCl(SMe2)] with cyclodiphosphazanes cis-{RP(micro-NtBu)}2 (1a-1d) produce binuclear gold(I) complexes of the type, [ClAu{RP(micro-NtBu)}2AuCl] (2 R=OC6H4OMe-o, 3R=OCH2CH2OMe, 4R=NEt2, 5R=NHtBu) in quantitative yield. A similar reaction between cis-{(o-MeOC6H4O)P(micro-NtBu)}2 (1a) and [AuCl(SMe2)] in a 1:1 molar ratio afforded the mono-nuclear complex [ClAu{(o-MeOC6H4O)P(micro-NtBu)}2] (6). Addition of two equivalents of CuX (X=Br, I) to the chloro derivative 2 leads to the formation of bromo, [BrAu{(o-MeOC6H4O)P(micro-NtBu)}2AuBr] (7), and iodo, [IAu{(o-MeOC6H4O)P(micro-NtBu)}2AuI] (8), derivatives through halogen exchange reactions. A tetranuclear gold(I) macrocycle [Au{(o-MeOC6H4O)P(micro-NtBu)}2]4(ClO4)4 (9) and a mononuclear gold(I) complex [Au({(o-MeOC6H4O)P(micro-NtBu)}2)2]ClO4 (10) were obtained, respectively, from 1:1 and 2:1 stoichiometric reactions between 1a and [Au(SMe2)2]ClO4. Molecular structures of complexes 4, 6, 7, 8 and 9 are confirmed by single-crystal X-ray diffraction studies. Interestingly, the crystal structure of the tetra-nuclear AuI macrocycle 9 reveals the encapsulation of one ClO4- anion inside the bowl shaped macrocyclic cavity through weak Au...O and C-H...O interactions.
两当量的[AuCl(SMe₂)]与环二磷腈cis-{RP(μ-NtBu)}₂（1a - 1d）反应，定量生成[ClAu{RP(μ-NtBu)}₂AuCl]类型的双核金（I）配合物（2，R = OC₆H₄OMe - o；3，R = OCH₂CH₂OMe；4，R = NEt₂；5，R = NHtBu）。顺式-{(o-MeOC₆H₄O)P(μ-NtBu)}₂（1a）与[AuCl(SMe₂)]以1:1摩尔比进行类似反应，得到单核配合物[ClAu{(o-MeOC₆H₄O)P(μ-NtBu)}₂]（6）。向氯代衍生物2中加入两当量的CuX（X = Br、I），通过卤素交换反应生成溴代物[BrAu{(o-MeOC₆H₄O)P(μ-NtBu)}₂AuBr]（7）和碘代物[IAu{(o-MeOC₆H₄O)P(μ-NtBu)}₂AuI]（8）。分别通过1a与[Au(SMe₂)₂]ClO₄按1:1和2:1化学计量比反应，得到四核金（I）大环化合物[Au{(o-MeOC₆H₄O)P(μ-NtBu)}₂]₄(ClO₄)₄（9）和单核金（I）配合物[Au({(o-MeOC₆H₄O)P(μ-NtBu)}₂)₂]ClO₄（10）。配合物4、6、7、8和9的分子结构通过单晶X射线衍射研究得以确定。有趣的是，四核AuI大环化合物9的晶体结构显示，通过弱的Au...O和C - H...O相互作用，一个ClO₄⁻阴离子被包封在碗状大环腔内。
