Wilton-Ely J D, Schier A, Mitzel N W, Schmidbaur H
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-85747 Garching, Germany.
Inorg Chem. 2001 Nov 19;40(24):6266-71. doi: 10.1021/ic001345l.
A series of dinuclear (phosphine)gold(I) complexes of the ambidentate 1,3,4-thiadiazoledithiolate ligand (SSS) were prepared in high yield from the corresponding (phosphine)gold(I) chlorides and K(2)(SSS) in methanol. While mononuclear components (R(3)P)AuCl with R(3) = Ph(3), Ph(2)Py, or Me(3) (1-3) gave open-chain complexes, the dinuclear components ClAu(Ph(2)P-E-PPh(2))AuCl with E = (CH(2))(6), (C(5)H(4))Fe(C(5)H(4)), or 1,4-CH(2)C(6)H(4)CH(2) afforded cyclic complexes (4-6). The products have been characterized by analytical and spectroscopic methods, and the crystal structures of 1-4 have been determined by single-crystal X-ray techniques. Crystals of 1 [(CH(2)Cl(2))(2)] and 2 (CH(2)Cl(2)) contain the molecules aggregated in strings with long and probably very weak intermolecular Au.S contacts. The P-Au-S groups are aligned parallel head-to-tail and shifted in opposite directions to reduce steric conflicts, thus ruling out aurophilic Au...Au bonding. By contrast, in crystals of 3 (CH(2)Cl(2)) with smaller tertiary phosphine ligands, the molecules are aggregated via short [3.0089(3) and 3.1048(5) A] and probably strong aurophilic bonding to give a two-dimensional network with tetranuclear units formed from four (Me(3)P)AuS moieties of four different molecules as the connecting elements. In these tetranuclear units (Me(3)P)AuS-, the P-Au-S axes are rotated against each other ("crossed swords") by 108.5 degrees (P2-Au2...Au2'-P2') or 116.9 degrees (P2-Au2...Au1'-P1'), respectively, to minimize steric conflicts. There is also significant bending of the P-Au-S axes to bring the metal atoms closer together: P1-Au1-S1 = 171.88(8) degrees and P2-Au2-S2 = 165.52(8) degrees. In the crystals of the cyclic complex 4 which contain no solvent molecules, the molecular units are aggregated in strings with short closed-shell interactions between the gold atoms of neighboring molecules [3.1898(3) A]. Because of the metallocyclic structure, the shielding of the gold atoms is reduced to allow aurophilic bonding as the P-Au-S groups are rotated against each other (crossed) by a dihedral angle P-Au...Au-P of 74.6 degrees.
通过相应的（膦）金（I）氯化物与K₂(SSS)在甲醇中反应，以高产率制备了一系列含两可配体1,3,4 - 噻二唑二硫醇盐（SSS）的双核（膦）金（I）配合物。单核组分（R₃P）AuCl（R₃ = Ph₃、Ph₂Py或Me₃，即1 - 3）生成开链配合物，而双核组分ClAu(Ph₂P - E - PPh₂)AuCl（E = (CH₂)₆、(C₅H₄)Fe(C₅H₄)或1,4 - CH₂C₆H₄CH₂）则得到环状配合物（4 - 6）。产物通过分析和光谱方法进行了表征，1 - 4的晶体结构通过单晶X射线技术测定。1 [(CH₂Cl₂)₂]和2 (CH₂Cl₂)的晶体中，分子以链状聚集，存在长且可能非常弱的分子间Au…S接触。P - Au - S基团头对头平行排列并向相反方向移动以减少空间冲突，从而排除了亲金性Au…Au键合。相比之下，在具有较小叔膦配体的3 (CH₂Cl₂)的晶体中，分子通过短的[3.0089(3)和3.1048(5) Å]且可能是强的亲金性键合聚集，形成二维网络，由四个不同分子的四个（Me₃P）AuS部分作为连接元素形成四核单元。在这些四核单元[(Me₃P)AuS⁻]₄中，P - Au - S轴彼此相对旋转（“交叉剑”），分别为108.5°（P2 - Au2…Au2' - P2'）或116.9°（P2 - Au2…Au1' - P1'），以最小化空间冲突。P - Au - S轴也有明显弯曲以使金属原子靠得更近：P1 - Au1 - S1 = 171.88(8)°，P2 - Au2 - S2 = 165.52(8)°。在不含溶剂分子的环状配合物4的晶体中，分子单元以链状聚集，相邻分子的金原子之间存在短的闭壳层相互作用[3.1898(3) Å]。由于金属环结构，金原子的屏蔽作用降低，使得当P - Au - S基团彼此相对旋转（交叉），二面角P - Au…Au - P为74.6°时能够形成亲金性键合。
