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Title:Preparation, Properties, and Catalytic Activity of Fluorous Phosphine Substituted Transition Metal Carbonyl Complexes
Author(s):Malosh, Thomas Joseph
Doctoral Committee Chair(s):Shapley, John R.
Department / Program:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(s):Chemistry, Inorganic
Abstract:Fluorous Biphasic Catalytic Systems are defined and introduced. The syntheses of perfluoroalkyl substituted tertiary phosphine compounds are examined in detail. Our approaches to the preparation and purification of the fluoroponytailed tertiary phosphines P(CH2CH2(CF2)5CF 3)3 and P(p-C6H4-CH 2CH2(CF2)7CF3)3 are discussed in depth. The compounds W(CO)5{P(CH2CH 2(CF2)5CF3)3}, W(CO) 5{P(n-octyl)3}, and W(CO)5{P( p-C6H4-CH2CH2(CF 2)7CF3)3}, were synthesized to probe the effects of ligation by perfluorocarbon substituted tertiary phosphines. W(CO)5{P(n-octyl)3} was prepared to provide a non-fluorous paradigm for W(CO)5{P(CH2CH 2(CF2)5CF3)3}. Infrared and 31P NMR data are compared and contrasted. The X-ray crystal structure of W(CO)5{P(p-C6H 4-CH2CH2(CF2)7CF3) 3} was determined. The fluorocarbon soluble, binuclear ruthenium(I) complexes [Ru(mu-O2CMe)(CO)2L], where L is a perfluoroalkyl substituted tertiary phosphine, P(p-C6H4 -CH2CH2(CF2)7CF3) 3 or P(CH2CH2(CF2)5CF 3)3 were synthesized to study the catalytic hydrogenation of ketones to alcohols under fluorocarbon/hydrocarbon biphasic conditions. Catalytic hydrogenation of actophenone to 1-phenylethanol was found to occur in the presence of [Ru(mu-O2CMe)(CO)2 {P(CH2 CH2(CF2)5CF3)3}] 2 or [Ru(mu-O2CMe)(CO)2{P(p-C 6H4-CH2CH2(CF2)7CF 3)3}]2. Under conditions favorable for hydroformylation, the catalytic isomerization of 1-dodecene to cis/trans-2-dodecene occurred in the presence of [Ru(mu-O2CMe)(CO)2{P( p-C6H4-CH2CH2(CF 2)7CF3)3)]2. The X-ray crystal structure of [Ru(mu-O2CMe)(CO)2{P(CH2CH 2(CF2)5CF3)3}]2 was determined. The triosmium carbonyl clusters Os3(CO)11 {P(CH2CH2(CF3)5CF3 )3} and Os3(CO)10{P(CH2CH 2(CF3)CF3)3}2 were synthesized to study the behavior of transition metal carbonyl clusters in fluorocarbon phases. Above 100°C, PPh3 will substitute for one or two carbonyl ligands to provide Os3(CO)10(PPh3){P(CH 2CH2(CF3)5CF3)3) and Os3(CO)9(PPh3)2{P(CH 2CH2(CF3)5CF3)3}. At circa 120°C and 1 atmosphere, Os3(CO) 11{P(CH2CH2(CF3)5CF 3)3} will activate H2 to form the unsaturated compound (mu-H)2Os3(CO)9{P(CH2CH 2(CF3)5CF3)3}. At circa 100°C, Os3(CO)11{P(CH 2CH2(CF3)5CF3)3} will react with HSiEt3 to form the mononuclear complex HOs(SiEt 3)(CO)3{P(CH2CH2(CF2) 5CF3)3}. The X-ray crystal structure of Os 3(CO)9(PPh3)2{P(CH2CH 2(CF3)5CF3)3}was determined. The fluorocarbon soluble, unsaturated triosmium cluster (mu-H)2Os 3(CO)9{P(p-C6H4-CH 2CH2(CF2)7CF3)3} was prepared and characterized. Ring-opening metathesis polymerization of norbornene occurs in the presence of (mu-H)2Os3(CO) 9{P(p-C6H4-CH2CH 2(CF2)7CF3)3}. A number of solvent systems were employed and results were analyzed with regard to both polymer production and triosmium cluster recovery. The polynorbornene was examined primarily by 13C{1H} NMR spectroscopy to determine the cis/trans ratio and also to determine the degree of cis/trans "blockiness".
Issue Date:2006
Description:212 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2006.
Other Identifier(s):(MiAaPQ)AAI3242929
Date Available in IDEALS:2015-09-25
Date Deposited:2006

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