Synthesis, structures and mass spectrometry of lanthanide nitrate complexes with tricyclohexylphosphine oxide

The complexes Ln(NO3)3(OPCy3)3(EtOH)x (Cy = cyclohexyl, C6H11x = 0 for Ln = Eu, Er, x = 0.5 for Ln = La, Nd and x = 1 for Ln = Tm, Yb) have been prepared by reaction of lanthanide nitrates with Cy3PO in ethanol. The single crystal X-ray structures for Ln = La, Nd, Eu, Er, Tm and Yb are reported. The structures for Ln = La–Eu have two molecules in the unit cell in which the nitrates are all bound as bidentate ligands. The unit cell for Ln = Er contains two distinct molecules; one with three bidentate nitrates and one with two bidentate and one monodentate nitrate. The Tm and Yb complexes have one molecule in the unit cell with two bidentate and one monodentate nitrate ligands. The monodentate nitrates are hydrogen bonded to ethanol in the Tm and Yb structures but not in the Er complex. The infrared spectra of the three classes of complex do not readily permit identification of the monodentate nitrate groups. Electrospray mass spectrometry indicates that redistribution/ionisation reactions occur in solution. Ions formed by solvolysis reactions are attributed to gas phase processes associated with the electrospray technique. Tandem mass spectrometry for the La, Ho and Yb complexes shows that in the gas phase loss of Cy3PO is the sole fragmentation pathway for all but the Yb complex where the higher energy required for initial fragmentation leads to a more complex fragmentation pattern.

Complexes of lanthanide nitrates with tricyclolhexylphosphine oxide show variations in the nitrate coordination as the Ln3+ ionic radii decrease. Tandem mass spectra are simple showing loss of Cy3PO from the complex apart for the Yb complex which undergoes more extensive fragmentation.Figure optionsDownload as PowerPoint slide