Bifunctional dithiophosphonate ligands were prepared from diols of the isomeric saturated cyclic alkane trans 1,2 cyclohexanediol. Such diols offer new perspectives in forming dithiophosphonates. Thus, reaction of (NH4)2[(S2P-1,4-C6H4OEt)2(trans-1,2-O,O'-C6H10)] with [AuCl(tht)] (tht = tetrahydrothiophene) (molar ratio 1:2) in THF led to the formation of a novel 27-membered metallatriangle of the type [Au2S2P-1,4-C6H4OEt)2(trans-1,2-O,O'-C6H10)]3 1 . Metallatriangles containing dinuclear units were hitherto unknown for gold and limited to very few metals in general.  Complex 1  exhibits two different types of intramolecular Au���Au interactions and is an ideal candidate for testing of oxidative addition (OA) products. We treated complex 1  with Br2, the dinuclear units circumvented isolable gold(II) formation. Instead, the entire assembly ruptured, forming a structurally characterized dinuclear gold(III) complex [{AuBr2}2(S2P-1,4-C6H4OEt)2(trans-1,2-O,O'-C6H10)]  2  as the stable major product. Complex 2  marks the first square planar gold(III) complex containing both a S-P-S chelate and halogen ligands bonded to the same Au(III) center.

Recent developments in gold(I) dithiophosphonate chemistry

244th National Meeting (2012)

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