Electronic Thesis and Dissertation Repository

Degree

Master of Science

Program

Chemistry

Supervisor

John F. Corrigan

Abstract

The manganese(II)‐palladium(II)‐sulfide complex [MnCl2(μ3‐S)2Pd2(dppp)2] 2 has been isolated from the reaction of [(dppp)PdCl2] with [Li(N,N’‐tmeda)]2[Mn(SSiMe3)4] 1 in a 2:1 ratio under mild conditions. The trimethylsilyl thiolate complex [(dppp)Pd(SSiMe3)2] 3 has been synthesized from the reaction of [(dppp)PdCl2] with Li[SSiMe3] as well as the reaction of [(dppp)Pd(OAc)2] with Li[SSiMe3] under mild conditions. The newly synthesized complex [(dppp)Pd(SSiMe3)2] 3 was used in reaction with the manganese(II) salt [(CH3CN)2Mn(OTf)2] to form the manganese(II)‐palladium(II)‐sulfide complex [Mn(OTf)(thf)2(μ‐S)2Pd2(dppp)2]OTf 4.

The reaction of the trimethylsilyl thiolate complex [PPh3AuSSiMe3] 5 with the manganese(II) salt [(CH3CN)2Mn(OTf)2] was explored and it was found that the previously characterized gold(I) sulfide complex [S(AuPPh3)3]Cl 6 was formed as the major product. The reaction of [Li(N,N’‐ tmeda)]2[Mn(SSiMe3)4] 1 with ferrocenoyl chloride was explored, however a ferrocene containing manganese(II) sulfide cluster could not be isolated. MS ESI studies revealed the molecular ion [Mn(Fc(C{O}S))3]‐ to be present in the reaction medium.

Single crystal X‐ray crystallography, elemental analysis, NMR spectroscopy, EPR spectroscopy, mass spectrometry, UV‐Vis absorption spectroscopy and photoluminescence emission spectroscopy were used as characterization techniques to analyze these complexes.

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