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Rauchfuss, Thomas B. Westmeyer, Mark David 2015-09-25T22:14:23Z 2015-09-25T22:14:23Z 10000-01-01 1998 1998 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 $\rm(C\sb3H\sb4PPh\sb2)Cp\sb3Fe\sb4(CO)\sb4RuCl\sb2(cymene).$. Made available in DSpace on 2015-09-25T22:14:23Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 9904620.pdf: 6956908 bytes, checksum: 17682aff251384a789f84f757ba2b459 (MD5) Previous issue date: 1998 Embargo set by: Seth Robbins for item 85699 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 168 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1998. http://hdl.handle.net/2142/84418 (MiAaPQ)AAI9904620 eng Chemistry, Inorganic New Materials Based on Metallodithiolenes, Fullerenes, and Cyclopentadienyl Iron Complexes text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.