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.