Abstract
Coordinative satn. of 4,4'-bipyrimidine (L) was achieved in W(CO)52-m4-LW(CO)4. Electrochem. and spectroscopic studies of the compd. and its anion radical exhibit a metal-to-ligand charge-transfer absorption max. at unexpected high energy, despite a small HOMO/LUMO gap. Inspection of band widths shows that large Franck-Condon contributions from the structurally flexible W(CO)5 fragments are responsible for the hypsochromic shift relative to the mononuclear chelate system. The propensity of polyfunctional p acceptor ligands towards complete coordinative satn. with electron-rich metal fragments is discussed. on SciFinder(R)
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