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The luminescence of neat crystals of (Me2PhP)AuX, where Me refers to methyl and X can be either Cl, Br or I, is investigated. The crystals show two emission systems, with the higher energy emission strongly similar to a corresponding system. However, a significant difference in the lower energy emissions in the two groups of compounds is observed. Results are in agreement with past research findings.

The structures of a series of nominally two-coordinate complexes are determined by single crystal X-ray diffraction. Spectroscopic studies show that the chloro complex crystallizes in dimeric and trimeric form. However, the nature of the crystallization process remains poorly understood. Spectroscopic data also suggest that the dimers dissocate when dissolved. Taken as a whole, the results indicate that self-association is common in (phosphine)gold(I) complexes where a small phosphine ligand inhibits such association.

Addition of 1 equiv of mercury(II) halides to Pt2(mu-dpm)2(CN)2 (dpm = bis(diphenylphosphino)methane) produces trinuclear complexes having a double A-frame structure. Synthesis of another trinuclear complex with an A-frame geometry involves an addition reaction between Pt2(mu-dpm)2(CN)2 and 1 equiv of ME2SAuCl. Spectroscopic and x-ray diffraction studies help characterize these complexes.

The preparation of a set of heterobinuclear d6/d8 molybdenum(0)/Palladium(II) complexes is accomplished by the interaction of (t-BuNC)2PdCl2 with mer-Mo(dpm-P, P') (dpm-P)(Co)3, where dpm refers to (bis-(diphenylphosphino) methane). This reaction occurs through the ring opening of the strained, four-membered chelate ring and transfer of an isocyanids ligand to the open coordination site on molybdenum. The two free phosphorus atoms of the dpm ligands entrap palladium to give rise to a (t-BuNc)(OC)3Mo(micro-dpm)2Pd unit.

The reaction between mer-Mo(dpm-P,P')(dpm-P)(CO)3 and Ph3PAuCl, where dpm = bis((diphenylphosphino)methane), is investigated. This reaction may form two products and is solvent dependent. The products, which include((OC)3MoCl(mu-dpm)2Au).2(C2H5)2O and ((dpm-O)2Mo(CO)2AuPPh3)(PF6).CH2Cl2.0.25CH3OH.0.25H2O, are binuclear complexes possessing Mo and Au, with the latter possessing a Mo-Au bond. Both complexes contain six-coordinate Mo(0) centers, with the latter having a pair of molybdenum d(sub pi) electrons forming a dative Mo-Au bond.

Electron deficient mixed-metal clusters, which are formed through the addition of (Pt2Au)3+ and (Pt2Hg)4+ cores to the Pt-Pt bond of Pt2(mu-dpm)2X2, exhibit luminescence. These cores have d10-s0 metal centers. The resulting clusters have 2-electron, 3-centered bonding within the trinuclear unit. Adducts absorption spectra are red shifted from the parent complexes and are different in details. Bindings in the cluster are analyzed using SCF-X-alpha-SW calculations.