Abstract

The reaction of the palladium(i) cluster Pd6(CO)6(OCOCMe3)6 having a cyclic metal core with gaseous nitrogen monoxide was studied by electronic absorption spectroscopy, IR spectroscopy, and GLC. In the system studied NO acts as an oxidant for both coordinated CO (oxidation to CO2) and NO itself, being reduced predominantly to N2. The product of nitrogen monoxide oxidation (NO2) was found in coordinated state in the new cluster Pd8(μ-CO)4(μ-NO2)4(μ-OCOCMe3)8. The cluster has an unusual structure: two tetranuclear metal chains Pd(μ-OCOCMe3)2Pd(μ-CO)2Pd(μ-OCOCMe3)2Pd are linked through four equivalent bridges -N(=O)-O- in such a way that a bulky cavity is formed.

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