Palladium(II) and Platinum(II) Compounds of 1,1′-Bis(phosphino)metallocene (M = Fe, Ru) Ligands with Metal–Metal Interactions

• DOI: 10.1021/om400494t
• Publication Date: 2013-09-11T14:22:10Z
• Authors: Kathryn M. Gramigna; Jeremy V. Oria; Chelsea L. Mandell; Margaret A. Tiede...; William G. Dougherty; Nicholas A. Piro; W. Scott Kassel; Benny C. Chan; Paula L. Diaconescu; Chip Nataro
• Keywords: Electronic effect; Oxidative addition

The reaction of [Pd(dtbpf)Cl2] (dtbpf = 1,1′-bis(di-tert-butylphosphino)ferrocene) with a chemical oxidant led unexpectedly to the formation [Pd(dtbpf)Cl]+. Further study found that variety reagents could be used abstract chloride ligand from yield solid-state structure suggests an Fe–Pd interaction. presence bulky tert-butyl groups is essential, as similar reactions [Pd(PP)Cl2] (PP other 1,1′-bis(phosphino)ferrocene ligands) results in [Pd(PP)(μ-Cl)]22+. analogous platinum compounds have also been investigated and appear behave manner. Similar type [M′(PP)(PR3)]2+ (M′ Pd, Pt, R Ph, Me) prepared, metal–metal interaction has observed. Steric electronic effects dictate these compounds. X-ray crystal structures were obtained for eight basis computational analysis DFT indicates weak, noncovalent between two metal centers. electrochemical properties examined by cyclic voltammetry typically show one oxidative wave either two-electron or one-electron reductive waves.