Reactions of {[Pd(μ-SC<sub>6</sub>F<sub>5</sub>)(μ-dppm)Pd](μ-SC<sub>6</sub>F<sub>5</sub>)}<sub>4</sub>·2O(C<sub>2</sub>H<sub>5</sub>)<sub>2</sub>. Crystal Structures of the Complexes [(Ph<sub>3</sub>P)Pd(μ-SC<sub>6</sub>F<sub>5</sub>)(μ-dppm)Pd(SC<sub>6</sub>F<sub>5</sub>)]·1.4CH<sub>2</sub>Cl<sub>2</sub> and [(Ph<sub>3</sub>P)Pd(μ-SC<sub>6</sub>F<sub>5</sub>)(μ-dppm)Pd(PPh<sub>3</sub>)]SO<sub>3</sub>CF<sub>3</sub>·2CH<sub>2</sub>Cl<sub>2</sub> and <i>ab </i><i>Initio</i> MO Calculations on the Model Systems [(H<sub>3</sub>P)Pd(μ-H<sub>2</sub>PCH<sub>2</sub>PH<sub>2</sub>)(μ-SH)Pd(PH<sub>3</sub>)]<sup>+</sup> and [(H<sub>3</sub>P)Pd(μ-H<sub>2</sub>PCH<sub>2</sub>PH<sub>2</sub>)Pd(PH<sub>3</sub>)]<sup>2+</sup>
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{[Pd(μ-SC6F5)(μ-dppm)Pd](μ-SC6F5)}4 reacts 1:4 with neutral ligands L to give [LPd(μ-SC6F5)(μ-dppm)Pd(SC6F5)] or 1:8 to form [LPd(μ-SC6F5)(μ-dppm)PdL]+ (dppm = bis(diphenylphosphino)methane). These binuclear complexes retain the palladium−palladium bond and the two dissimilar bridging ligands, as demonstrated by the X-ray structural determinations carried out on [(Ph3P)Pd(μ-SC6F5)(μ-dppm)Pd(SC6F5)]·1.4CH2Cl2 and [(Ph3P)Pd(μ-SC6F5)(μ-dppm)Pd(PPh3)]SO3CF3·2CH2Cl2. Ab initio calculations on the model systems [(H3P)Pd(μ-H2PCH2PH2)(μ-SH)Pd(PH3)]+ and [(H3P)Pd(μ-H2PCH2PH2)Pd(PH3)]2+ show that the metal−metal bond arises mainly from interactions between palladium sp orbitals, which also play a predominant role in the binding with the sulfur bridge.
