Photochemical Generation of High Spin Clusters in Solution: (Cyclopentadienyl−Vanadium)mOn

Abstract

Organometallic clusters containing oxygen atoms, (CpV)mOn (Cp = C5H5), are generated by photochemical reaction of CpV(CO)4 in CH2Cl2 solution with control of oxygen concentration. Mass spectra of single batch reactions exhibit strong signals assigned to low mass oxide clusters: (CpV)4O4, (CpV)5O6, and (CpV)6On (n = 6−8). Successive addition of reactant solution into the photochemical reaction vessel shows the addition of (CpV)m‘ to the low mass oxide clusters, producing (CpV)mOn (m ≫ n = 4−7). The magnetic susceptibility (χg) of the mixture of the former low mass products shows antiferromagnetic behavior, while that of the latter high mass products is as high as 4.6 × 10-4 cm3 g-1 at 10 K. The additional part due to high mass products behaves ferromagnetically at temperatures higher than 70 K.