Diversity in the structural chemistry of (phosphine)gold(I) 1,3,4-thiadiazole-2,5-dithiolates (bismuthiolates I)

J. D.E.T. Wilton-Ely, A. Schier, N. W. Mitzel, H. Schmidbaur

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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 K2(SSS) in methanol. While mononuclear components (R3P)AuCl with R3 = Ph3, Ph2Py, or Me3 (1-3) gave open-chain complexes, the dinuclear components ClAu(Ph2P-E-PPh2)AuCl with E = (CH2)6, (C5H4)Fe(C5H4), or 1,4-CH2C6H4CH2 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 [(CH2Cl2)2] and 2 (CH2Cl2) 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 (CH2Cl2) with smaller tertiary phosphine ligands, the molecules are aggregated via short [3.0089(3) and 3.1048(5) Å] and probably strong aurophilic bonding to give a two-dimensional network with tetranuclear units formed from four (Me3P)AuS moieties of four different molecules as the connecting elements. In these tetranuclear units [(Me3P)AuS-]4, the P-Au-S axes are rotated against each other ("crossed swords") by 108.5° (P2-Au2···Au2′-P2′) or 116.9° (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)° and P2-Au2-S2 = 165.52(8)°. 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) Å]. 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°.

Original languageEnglish
Pages (from-to)6266-6271
Number of pages6
JournalInorganic Chemistry
Issue number24
StatePublished - 19 Nov 2001
Externally publishedYes


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