Dinoi C.Sözen P.Taban G.Demir D.Demirhan F.Prikhodchenko P.Gun J.Lev O.Daran J.-C.Poli R.2024-07-222024-07-22200714341948http://akademikarsiv.cbu.edu.tr:4000/handle/123456789/19323Zinc reduction of Cp*2W2O5 in an acidified water-methanol medium affords the green 3-electron trinuclear cluster [Cp*3W3O4(OH)2]2+, isolated and crystallographically characterized as the triflate salt, 1. Upon exposure to air, this complex is oxidized to a related 2-electron cluster, [Cp*3W3O6]+, which was crystallized and characterized in three different salts, 2-4. The 3-electron cluster exhibits a near-tetragonal frozen-glass EPR spectrum, and it shows evidence of coupling of the unpaired electron to only one of the three W atoms. The two-electron cluster is diamagnetic. An electrospray ionization MS n study revealed a stepwise expulsion of neutral [Cp*WO 2] units as the main fragmentation process. DFT calculations unveiled the intimate details of the electronic structures of these complexes and fully rationalized the structural and spectroscopic properties. © Wiley-VCH Verlag GmbH & Co. KGaA, 2007.EnglishAll Open Access; Green Open AccessElectron spin resonance spectroscopyElectronic structureElectrospray ionizationReductionTungsten% reductionsAcidified watersDensity-functional calculationsElectron clusterMetal clusterO ligandsTriangular clustersTrinuclear clusterWater-methanolZinc reductionDensity functional theoryArticle10.1002/ejic.200700419