Mass spectrometric studies of some bis(η5-pentamethylcyclopentadienyl)metal derivatives, and related complexes

Add time:08/04/2019    Source:sciencedirect.com

A series of bis(pentamethylcyclopentadienyl)metal derivatives, and related complexes, including [Mo(C5Me5)2X2] (X2 = H2, Cl2, I2 or O), [W(C5Me5)2X2] (X = H, Cl or CH3), [W(C5Me5)(C5Me4CH2)Cl], [Re(C5Me5)2], [Re(C5Me5)(C5Me4CH2], [Re(C5Me5)2(NO)], [Rh(C5Me5)(C5Me5H)], [Rh(C5Me5)3][BF4], [{rh(C5Me5)X2}2] (X = Cl, Br or I), and [M(C5Me5)2] (M = Fe or Bu) have been investigated by mass spectrometry using different ionization techniques, viz. electron impact (EI), chemical ionization (CI) and fast-atom bombardment (FAB). The fragmentation pathways were confirmed by observation of the metastable transitions for the spectra obtained by EI. For both FAB and EI spectra, the identities of the molecular iosn and najor metal-containing fragment ions were confirmed by fitting to computer-simulated isotopic abundance patterns. Intramolecular oxidative addition reactions, to form a cyclometallated species via sixteen-electron intermediates, were observed for rhenium, molybdenum and tungsten complexes in the gas phase; these parallel known behaviour in solution. In contrast of iron, ruthenium and rhodium, which do not achieve a sixteen-electron configuration, fragment via the loss of methyl groups.

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