The production and photodissociation of iron–sulfur cluster ions

Abstract

Iron–sulfur cluster ions FenSm+ (n=1–13, m=1–13) were produced by direct laser ablation on a solid sample containing a mixture of iron and sulfur powder. UV photodissociation of the cluster ions was studied with a tandem time-of-flight mass spectrometer. It was found that all the cluster ions with compositions of m=n, m=n−1, or m=n+5 were relatively more abundant, indicating that they were stable. The photodissociation results of the FenSm+ ions showed that, for parent ions with n≪m, the main channels were sequential losses of neutral S atoms until n∼m, while for parent ions with n∼m, the main product ions had compositions of smaller m=n or m=n−1. From these experimental results, it is proposed that the FenSn+ cluster ions might have structures similar to those of the FenS*n cores in iron–sulfur proteins, while the FenSm+ (m≳n) cluster ions could be considered to have structures with the FenSn+ cores surrounded by some peripheral S atoms.