University of Illinois Urbana-Champaign

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

Westmeyer, Mark David

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Description

Title
New Materials Based on Metallodithiolenes, Fullerenes, and Cyclopentadienyl Iron Complexes
Author(s)
Westmeyer, Mark David
Issue Date
1998
Doctoral Committee Chair(s)
Rauchfuss, Thomas B.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Inorganic
Language
eng
Abstract
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 $\rm(C\sb3H\sb4PPh\sb2)Cp\sb3Fe\sb4(CO)\sb4RuCl\sb2(cymene).$.
Graduation Semester
1998
Type of Resource
text
Permalink
http://hdl.handle.net/2142/84418

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