10.1021/om980665y.s001 Brian T. Sterenberg Brian T. Sterenberg Hilary A. Jenkins Hilary A. Jenkins Richard J. Puddephatt Richard J. Puddephatt Complexes with Platinum−Iridium Bonds:  Stepwise Formation of a PtIr<sub>2</sub> Cluster Complex American Chemical Society 1998 PF Ph 2 PCH 2 PPh 2 PtIr 2 group dppm PtIr 2 Cluster Complex PtIr 2 CO NMR cluster 1998-12-24 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Complexes_with_Platinum_Iridium_Bonds_Stepwise_Formation_of_a_PtIr_sub_2_sub_Cluster_Complex/3783312 The reaction of [Pt(dppm)<sub>2</sub>]Cl<sub>2</sub> (dppm = Ph<sub>2</sub>PCH<sub>2</sub>PPh<sub>2</sub>) with [Ir(CO)<sub>4</sub>]<sup>-</sup> and dppm in a 1:2:1 ratio leads in a multistep reaction to the new heteronuclear cluster complex [PtIr<sub>2</sub>(CO)<sub>2</sub>(μ-CO)(μ-dppm)<sub>3</sub>], which contains a triangle of metal atoms with each edge bridged by a dppm ligand and in which only the platinum atom is coordinatively unsaturated. The initial step in the reaction leads to formation of the neutral and cationic binuclear complexes [PtIrCl(CO)<sub>2</sub>(μ-dppm)<sub>2</sub>] and [PtIr(CO)<sub>3</sub>(μ-dppm)<sub>2</sub>]<sup>+</sup>, respectively. The binuclear complexes then react with additional [Ir(CO)<sub>4</sub>]<sup>-</sup> to form the cluster [PtIr<sub>2</sub>(CO)<sub>4</sub>(μ-CO)(μ-dppm)<sub>2</sub>] by insertion into a Pt−P linkage; this cluster can exist in two isomeric forms, each containing a triangular PtIr<sub>2</sub> group with the Ir−Ir and one Pt−Ir edge bridged by dppm ligands but differing in stereochemistry. These isomers equilibrate slowly at room temperature, and each reacts easily with dppm to form the final cluster complex [PtIr<sub>2</sub>(CO)<sub>2</sub>(μ-CO)(μ-dppm)<sub>3</sub>]. The structures of the complexes [PtIr<sub>2</sub>(CO)<sub>2</sub>(μ-CO)(μ-dppm)<sub>3</sub>], [PtIr(CO)<sub>3</sub>(μ-dppm)<sub>2</sub>][PF<sub>6</sub>], and one isomer of [PtIr<sub>2</sub>(CO)<sub>4</sub>(μ-CO)(μ-dppm)<sub>2</sub>] have been determined crystallographically, and the reaction sequence has been determined by monitoring reactions through NMR methods.