Fast atom bombardment mass spectrometry of neutral methanide and ionic carbene platinum(II) derivatives

The fast atom bombardment mass spectra of a series of neutral methanide and ionic carbene platinum(II) complexes of formula dPePtL2 and [dPePt(LH)2](BF4)2 (dPe = (C6H5)2PCH2CH2P(C6H5)2; L = C(OCH3)‐NCH3, C(OCH3)  NC6H11, C(OCH3)  NC6H4p CH3), respectively are reported. Glycerol, 3‐mercapto‐1,2‐propanediol, bis (2‐hydroxyethyl)sulphide, 3‐nitrobenzyl alcohol, and 2,4‐di‐tert‐pentylphenol have been used as matrices. Neutral and ionic derivatives containing the same ligand behave similarly and give the same quasi‐molecular [dPePtL(L + H)]+ ion by different primary processes. Stepwise breakdown of the ligands L with retention or further loss of atoms or molecules of hydrogen is observed for all these complexes, followed by ejection of radicals from the dPe ligand. Elimination of CH3OH from [dPePtL(L + H)]+ also occurs. The highest ionic yields of both neutral methanide and ionic carbene complexes are observed in 3‐mercapto‐1,2‐propanediol, in bis(2‐hydroxyethyl)sulphide, and in 3‐nitrobenzyl alcohol with respect to glycerol. The [dPePt(LH)2]2+ doubly charged ions are present in the spectra obtained with 3‐nitrobenzyl alcohol and are rather strong when L is C(OCH3)  NCH3 and C(OCH3)  NC6H4p CH3. Substitution of ligands L with a molecule or with a fragment of a sulphur containing matrix takes place very seldom with this series of complexes.