The syntheses and vibrational spectra of bis(carbonyl)platinum(II) fluorosulfate, Pt(CO) 2(SO 3F) 2, and bis(carbonyl)palladium(II) fluorosulfate, Pd(CO) 2(SO 3F) 2

Abstract

Reductive carbonylation of platinum(IV) tetrakis(fluorosulfate), Pt(SO 3F) 4, in fluorosulfuric acid at 80 °C with a CO pressure of 1–2 atm resulted in the quantitative formation of creamy white bis(carbonyl)platinum(II) fluorosulfate, Pt(CO) 2(SO 3F) 2. The corresponding bis(carbonyl)palladium(II) fluorosulfate, Pd(CO) 2(SO 3F) 2, has been formed from solid Pd IIPd IV(SO 3F) 6 at room temperature and a CO pressure of 0.5 atm as a yellow solid that was thermally stable up to 117 °C. Both compounds gave nearly identical IR and Raman spectra, which suggests a cis-square-planar configuration. The average CO stretching frequencies were at 2217 and 2201 cm −1 for Pd(CO) 2(SO 3F) 2 and Pt(CO) 2(SO 3F) 2, respectively. They are unusually high and suggest substantially reduced π-back-donation. Pd(CO) 2(SO 3F) 2 is the first example of a thermally stable mononuclear bis(carbonyl) derivative of dipositive palladium.