Abstract
Dinuclear gold (I) "open ring" complexes of the type [Au2(MNT)(PR3)2] have been synthesized. The trialkylphosphines used include: PMe3, P(OPh)3, PEt3, PPh3 and PCy3. The molecular structure of these complexes, as determined through X-ray crystallography, show an MNT unit bridging two gold centers and a trialkylphosphine ligand coordinated to each gold(I) atom. One of the gold centers exhibits linear two-coordinate geometry, while the other gold(I) atom is an irregular three-coordinate center. The synthesis of analogous "open ring" complexes using tolyldithiol and xylenedithiol as bridging ligands has produced the complexes Au4(tolyldithiol)2(PEt3)2 and Au2(xylenedithiol)(PPh3)2. The former is a tetranuclear species containing a dinuclear bis(dithiolene) anion "capped" by two [AuPEt3]+ units. The structure of Au2(xylenedithiol)(PPh3)2 shows a typical "open ring" complex with two linear S-Au-P chains trans to each other. Additionally, the synthesis and characterization of dinuclear gold(I) "ring" complexes of the type Au2(i-MNT)[Ph2P(CH2)nPPh2] (n= 2, 4), Au2(i-MNT)[Ph2P(CH)2PPh2] and Au2(i-MNT)[Ph2P(CH2 )2AsPh2] is reported. The molecular structure of Au2(i-MNT)[Ph2P(CH)2PPhJ features two linear two-coordinate gold® centers bridged by the i-MNT ligand on one side and by a bis(diphosphine) ligand on the other. The same general configuration is expected for the other "ring" complexes. The study of dinuclear "ring" complexes with the MNT ligand has produced interesting results in the area of gold-olefin chemistry. The synthesis and characterization of Au4(MNT)[Ph2P(CH)2PPh2 ](Cl)2 is reported. The latter complex is a tetranuclear species containing an interaction of one of the gold(I) centers with the olefinic portion of one of the bis(diphosphine) ligands. Attempts to synthesize additional gold-olefin complexes has produced [Au(Ph2P(CH)2PPh2)2][Au(MNT)(PPh3)] and [Au(Ph2P(CH)2PPh2)2][Au(MNT)2]. The structures of these two complexes is described.
Davila, Rosa Maria (1993). Synthesis and characterization of dinuclear gold(I) complexes containing dithiolates and phosphines or bis(Diphosphine) donor ligands. Texas A&M University. Texas A&M University. Libraries. Available electronically from
https : / /hdl .handle .net /1969 .1 /DISSERTATIONS -1519683.