Supporting Information

Probing the Reactivity and Radical Nature of Oxidized Transition Metal-Thiolate Complexes by Mass Spectrometry

Mei Lu,1 J. Larry Campbell,2* Rajat Chauhan3, Craig A. Grapperhaus,3* Hao Chen1*

1Center for Intelligent Chemical Instrumentation, Department of Chemistry and Biochemistry, Ohio University, Athens, OH 45701, United States,

2AB Sciex, 71 Four Valley Drive, Concord, Ontario L4K 4V8, Canada,

3Department of Chemistry, University of Louisville, Louisville, Kentucky 40292,

United States,

Figure 1S. Schemes showing the 2000 QTRAP® instrument modified for carrying out the ion/molecule reactions a) in q2 at low pressure and b) at atmospheric pressure during the ESI process.

Figure 2S. MS spectra showing the tested ion/molecule reactions of a) 2,4,6-triphenylpyrylium (m/z 309) with propylamine; b) [insulin+5H]5+ ion (m/z 1147) with propylamine and c) GS+. distonic ion (m/z 307) with CH3SSCH3.

Figure 3S. MS spectrum showing the ion/molecule reaction of [RuL3]- (m/z 981) with C2H4.

Figure 4S. MS spectra showing the low-pressure gas phase reactions of ethylene with the ion of a) m/z 903 generated from [RuL3]+ (m/z 981) by loss of benzene; b) sulfur oxidized product [RuL3+O]+ (m/z 997); c) m/z 688 generated from [RuL3]+ (m/z 981) by loss of LH; and d) m/z 872 generated from [RuL3]+ (m/z 981) by loss of PhS• radical.

Figure 5S. CID MS/MS spectra of the atmospheric-pressure ion/molecule reaction product ions of a) [RuL3.CH3S•]+ (m/z 1028); b) [RuL3.2CH3S•]+ (m/z 1075); c) [ReL3.CH3S•]+ (m/z 1113) and d) [NiL2.CH3S•]+ (m/z 691).

Figure 6S. CID MS/MS spectra of the atmospheric-pressure reaction product ions of a) [RuL3.C2H5S•]+ (m/z 1042) and b) [RuL3.2C2H5S•]+ (m/z 1103). ESI-MS spectra of c) ReL3 and d) NiL2 in the presence of C2H5SSC2H5 including 1 mM LiOTf.

Figure 7S. ESI-MS spectra of a) [PPN]+[RuL3]-, b) ReL3 and c) NiL2 in the presence of 1% DMPO and 1 mM LiOTf. Note that no products from the addition of oxidized metal thiolate complex ions with spin trap DMPO (MW 113 Da) are formed.

Figure 8S. CID MS/MS spectra of the reaction product ions of a) [RuL3.CH3S•-H]+ (m/z 1027) and b) [RuL3.CD3S•-H]+ (m/z 1030).