Department of Chemistry, #2252, University of Tennessee @ Chattanooga, Chattanooga, TN 37403, USA.
Dalton Trans. 2012 Aug 7;41(29):8745-61. doi: 10.1039/c2dt30747b. Epub 2012 Jun 25.
Platinum(II) and palladium(II) complexes of the trithiacrown [9]aneS(3) containing a range of Group 15 donors are reviewed. These complexes have the general formula M([9]aneS(3))(L(2)) where L represents at least one Group 15 donor. Complexes involving pnictogens, with the exception of bismuth, are observed. The complexes generally have an elongated square pyramidal geometry with a long distance interaction to the third sulphur of the [9]aneS(3) which forms the apex of the square pyramid. This axial metal-sulphur distance is quite sensitive to the donor properties of L. Poorer donors such as Sb and As ligands show short axial distances whereas the better N donor ligands show longer distances. Pt(II) complexes of the formula Pt([9]aneS(3))(EPh(3))(2) (E = P, As, Sb) show a considerable distortion towards a trigonal bipyramidal geometry due to intramolecular π-π interactions. Over seventy of these types of complexes have been crystallographically characterized and are discussed in this article. Other unique features of the complexes, including NMR spectroscopy, redox chemistry, and electronic spectroscopy, are also discussed.
综述了一系列含 Group 15 给体的三硫杂[9]轮烷 S(3) [Pt(II) 和 Pd(II)]配合物。这些配合物具有通式M([9]aneS(3))(L(2))，其中 L 代表至少一个 Group 15 给体。除铋外，还观察到涉及磷属元素的配合物。这些配合物通常具有拉长的四方锥几何形状，与 [9]aneS(3) 的第三个硫原子存在长距离相互作用，该硫原子形成四方锥的顶点。这个轴向金属-硫距离对 L 的给体性质非常敏感。Sb 和 As 等较差的给体配体显示较短的轴向距离，而较好的 N 给体配体则显示较长的距离。Pt(II)配合物Pt([9]aneS(3))(EPh(3))(2)（E = P、As、Sb）由于分子内π-π相互作用，显示出相当大的向三角双锥几何形状的扭曲。超过 70 种这类配合物已通过晶体学进行了表征，并在本文中进行了讨论。配合物的其他独特特征，包括 NMR 光谱、氧化还原化学和电子光谱，也进行了讨论。
