Mixed metal complexes of the type [Pt(κ2-2-C6R4PPh2) (PPh3) (μ-2-C6R4PPh2)AuCl] (R = H, F) can be prepared by treatment of cis-[Pt(κ2-C6R4PPh2)2] with [AuCl(PPh3)]. Under similar reaction conditions, the trans isomer of [Pt(κ2-C6F4PPh2)2] is unreactive. Computational studies have been performed to provide insights into the reasons for this difference in reactivity. Density Functional Theory (DFT) calculations show that formation of an AuCl adduct of [Pt(κ2-2-C6R4PPh2)2] is favoured over nucleophilic addition of PPh3 to Pt as the initial step of the reaction, and reveal the required energy of the cis and trans isomers of the bis-chelate [Pt(κ2-2-C6R4PPh2)2] in forming the mixed metal Pt-Au compounds. NBO analysis sheds more light on the bonding orbitals of the cis and trans isomers, suggesting that the Pt-P bonds in the cis isomer are more labile.
Bibliographical noteFunding Information:
LZ gratefully acknowledges the financial support of the Marie Curie Industrial-Academic Partnership Pathways project QUASINANO ( REA-FP7-PEOPLE-2009- IAPP/251149 ).
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All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
- Materials Chemistry