New Materials Based on Metallodithiolenes, Fullerenes, and Cyclopentadienyl Iron Complexes

We focused on the development of methods to functionalize a metal cluster through cyclopentadienyl (Cp) ligands. The cluster, $\rm Cp\sb4Fe\sb4(CO)\sb4,$ is prepared from the thermolysis of xylene solutions of $\rm Cp\sb2Fe\sb2(CO)\sb4$ and PPh$\sb3$ to yield primarily $\rm Cp\sb4Fe\sb4(CO)\sb4$ together with smaller amounts of $\rm(C\sb5H\sb4Ph)CP\sb3Fe\sb4(CO)\sb4$ and $\rm Cp\sb3Fe\sb3(CO)\sb3(PPh\sb2).$ Cluster, $\rm Cp\sb4Fe\sb4(CO)\sb4,$ can be alkylated and arylated using organolithium reagents to give the derivatives $\rm(C\sb5H\sb4R)Cp\sb3Fe\sb4(CO)\sb4.$ This reaction is competitive with reduction of $\rm Cp\sb4Fe\sb4(CO)\sb4$ by the organolithium reagent. A more versatile method for functionalizing $\rm Cp\sb4Fe\sb4(CO)\sb4$ involves its deprotonation using lithium diisopropyl amide (LDA) followed by treatment with electrophiles to give \rm(C\sb5H\sb4X)Cp\sb3Fe\sb4(CO)\sb4 (X=C(OH)HCH\sb3, CO\sb2H, CHO, SPh, PPh\sb2). Excess of LDA gave increased amounts of the di- and even trifunctionalized derivatives $\rm(C\sb5H\sb4X)\sb{x}Cp\sb{4-x}Fe\sb4(CO)\sb4$ (x = 2, 3). The reactivity of the lithiated clusters towards organic electrophiles led us to investigate routes to dicubane clusters. Treatment of $\rm(C\sb5H\sb4CHO)Cp\sb3Fe\sb4(CO)\sb4$ with the lithiated cluster gave the dicluster $\rm\lbrack(C\sb5H\sb4)Cp\sb3Fe\sb4(CO)\sb4\rbrack\sb2CHOH.$ The use of the cluster as a ligand was demonstrated by the synthesis of the adducts $\rm(C\sb5H\sb4PPh\sb2ML\sb{n})Cp\sb3Fe\sb4(CO)\sb4,$ where ML$\rm\sb{n}$ = RuCl$\sb2$(cymene), IrCl(1,5-$\rm C\sb8H\sb{12}).$ Single crystal X-ray diffraction was employed to characterize $\rm\lbrack(C\sb5H\sb4)Cp\sb3Fe\sb4(CO)\sb4\rbrack\sb2CHOH$ and $\rm(C\sb3H\sb4PPh\sb2)Cp\sb3Fe\sb4(CO)\sb4RuCl\sb2(cymene).$.

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

• Westmeyer, Mark David

Contributors dc:contributor

• Rauchfuss, Thomas B.

• Chemistry, Inorganic

Language dc:language

eng

Identifier

(MiAaPQ)AAI9904620

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84418