Synthesis and Reactivity of Polysulfido Metal Complexes

The final area of thesis research is the investigation iridium polysulfido complexes. Desulfurization of (NBun4 )Ir(S6)3 with excess PPh3 yields a 30 e-- dimer Ir2S2(PPh4) 4. Crystallographic analysis of Ir2S2(PPh 4)4 reveals a bitetrahedral structure with a pair of mu-S atoms. Two equiv of H2 add to Ir2S2(PPh 4)4 to yield Ir2S(SH)H3(PPh3) 4. The first addition of H2 to Ir2S2(PPh 4)4 proceeds homolytically while the second addition proceeds formally heterolytically. One equiv of H2 adds to Ir2S 2(PPh4)4 to yield Ir2S2H 2(PPh3)4. Low temperature H2 addition to Ir2S2(PPh4)4 reveals an intermediate. This intermediate is a kinetic isomer of compound Ir2S(SH)H 3(PPh3)4. The conversion of this intermediate to Ir2S(SH)H3(PPh3)4 is a first-order reaction with an approximate rate constant of 5 x 10-5 s-1 at -20°C. With a 50 fold excess of H2, the production of Ir2S(SH)H3(PPh 3)4 by the addition of H2 to Ir2S 2H2(PPh3)4 is also a first-order reaction with an approximate rate constant of 3 x 10-5 s -1.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2015

Author dc:creator

• Pafford, Robert Joseph, IV

Contributors dc:contributor

• Rauchfuss, Thomas B.

• Chemistry, Inorganic

Language dc:language

eng

Identifier

(MiAaPQ)AAI9990103

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84492