| Abstract
| - A series of new complexes incorporating thefunctionalized tetrathiafulvalene (TTF) ligandsortho-(CH3)2(P(C6H5)2)2TTF (o-P2) and(P(C6H5)2)4TTF(P4) have been prepared and studied by fast atom bombardment massspectrometry(FABMS). The mononuclear o-P2 complexes[M(o-P2)2](BF4)2(M = Fe, Pd, Pt) and[Co(o-P2)2(NCCH3)2](BF4)2were synthesized from reactions of the free ligand with the fullysolvated BF4- salts[M(NCCH3)n](BF4)2(M =Fe, Co, n = 6; M = Pd, Pt, n = 4). Thedinuclear P4 complex,[Pt2(P4)(NCCH3)4](BF4)4,was produced byreacting the free ligand withPtCl2(NC7H5)2followed by abstraction of the chlorides with AgBF4 inacetonitrile.Reaction of[Pd(NCCH3)](BF4)2 with1 equiv of P4 produces the polynuclear compound formulatedas[Pd(P4)]n(BF4)2nwhich was characterized by infrared, 1H, and31P{1H} NMR spectroscopies andelemental analysis.The use of FABMS in this study was undertaken in order toelucidate the chemical options of multiply chargedcations in the desorption process from the liquid matrix to the gasphase. The use of additives to the FAB matrix(m-nitrobenzyl alcohol) was demonstrated for the P4complexes which do not give spectra in this medium due toa high positive net charge. The addition of triflic acid (HOTf orCF3SO3H) to the FAB matrix/analytesolutionwas shown to assist in the MS analysis of cationic complexes with up tosix charges and a mass range up tom/z4000. When HOTf is added, bound OTf- anions areformed and are attached to the cationic complex, loweringthe net charge to +1. The method of using matrix additives asopposed to chemically synthesizing the OTf-compounds is a convenient in situ method which produces species thatare capable of being analyzed by FABMS.
- The characterizationof mononuclear and polynuclear transition-metal complexes with di- andtetra-phosphine-functionalized tetrathiafulvalene ligands by fast atombombardment mass spectrometry is reported. The chemical behaviorof multiply charged species in the FAB experiment is considered,including a simple approach to obtaining meaningful spectra of suchtransition-metal complexes which were previously refractory to FABMS.The use of triflic acid (HOTf orCF3SO3H) as a matrix additive is shown toassist in the analysis of highly charged extended structures such as[M(P4)]n2n+(M = Pd).
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