Reactivity of carbon dioxide with organosamarium compounds and the synthesis and reactivity of solvent free organolanthanide metallocene cations.

摘要

The first part of this dissertation describes studies of the reactivity of organosamarium compounds with CO{dollar}sb2.{dollar} Two strategies for CO{dollar}sb2{dollar} activation were utilized: reduction using a Sm(II) organometallic reagent, namely ({dollar}rm Csb5Mesb5)sb2Sm(THF)sb2,{dollar} and insertion of CO{dollar}sb2{dollar} into Sm(III)-C and Sm(III)-N bonds.; Investigation of the chemical reduction of CO{dollar}sb2{dollar} utilizing the strongly reducing ({dollar}rm Csb5Mesb5)sb2Sm(THF)sb2{dollar} resulted in the direct reductive dimerization of CO{dollar}sb2{dollar} producing an oxalate dianion (({dollar}rm Osb2CCOsb2)rbracksp{lcub}2-{rcub}{dollar} in high yield. The analogous reaction with COS resulted in reductive disproportionation and produced the dithiocarbonate dianion, COS{dollar}sb2sp{lcub}2-{rcub}{dollar} and CO.; Once the reactivity of CO{dollar}sb2{dollar} with divalent organosamarium metallocenes was defined, the investigation of CO{dollar}sb2{dollar} insertion reactivity with trivalent organosamarium metallocenes was undertaken. The reaction of CO{dollar}sb2{dollar} with the bimetallic compound ({dollar}rm Csb5Mesb5)sb2Sm(mu{dollar}-{dollar}etasp1{lcub}:{rcub}etasp1{dollar}-{dollar}rm Nsb2Phsb2){dollar} resulted in the production of the asymmetric product ({dollar}rm Csb5Mesb5)sb2Smlbrack mu{dollar}-{dollar}etasp2{lcub}:{rcub}etasp1{dollar}-PhNN(CO{dollar}sb2{dollar})Ph) Sm({dollar}rm Csb5Mesb5)sb2{dollar}(THF) in high yield.; Further insertion chemistry of CO{dollar}sb2{dollar} with organosamarium compounds was demonstrated by clean insertion reactions with Sm-R bonds of monometallic ({dollar}rm Csb5Mesb5)sb2{dollar}Sm-R compounds (R = {dollar}rm Csb6Hsb5, CHsb2CHCHsb2Rspprime{dollar}). COS and CS{dollar}sb2{dollar} were also found to cleanly insert into the Sm-R bonds producing analogous products.; The second part of this dissertation describes the preparation and reactivity of solvent free lanthanide metallocene cations of general formula (({dollar}rm Csb5Mesb5)sb2Lnrbracklbrack BPhsb4rbrack.{dollar} Research was directed toward developing a solvent free samarium metallocene analogous to (({dollar}rm Csb5Mesb5)sb2Sm(THF)sb2rbracklbrack BPhsb4rbrack.{dollar} Reduction of AgBPh{dollar}sb4{dollar} by unsolvated divalent ({dollar}rm Csb5Mesb5)sb2Sm{dollar} in arene solvents was successful in generating (({dollar}rm Csb5Mesb5)sb2Smrbracklbrack BPhsb4rbrack.{dollar} The reaction of (({dollar}rm Csb5Mesb5)sb2Smrbracklbrack BPhsb4rbrack{dollar} with KC{dollar}sb4{dollar}Me{dollar}sb5{dollar} provided a new route to ({dollar}rm Csb5Mesb5)sb3Sm.{dollar}; New synthetic routes to (({dollar}rm Csb5Mesb5)sb2Lnrbracklbrack BPhsb4rbrack{dollar} which did not depend on divalent ({dollar}rm Csb5Mesb5)sb2Ln{dollar} were developed. Syntheses utilizing Ln(III) precursors were developed involving protonation reactions of ({dollar}rm Csb5Mesb5)sb2Ln(etasp3{dollar}-CH{dollar}sb2{dollar}CHCH{dollar}sb2{dollar}) with Et{dollar}sb3{dollar}NHBPh{dollar}sb4{dollar} in non-coordinating solvents to cleanly produce (({dollar}rm Csb5Mesb5)sb2Lnrbracklbrack BPhsb4rbrack.{dollar} The reaction of (({dollar}rm Csb5Mesb5)sb2Ndrbracklbrack BPhsb4rbrack{dollar} with KC{dollar}sb5{dollar}Me{dollar}sb5{dollar} produced ({dollar}rm Csb5Mesb5)sb3Nd{dollar} in sufficiently high quantities and purity to allow full characterization for the first time.; In order to fully utilize ({dollar}rm Csb5Mesb5)sb2Ln(etasp3{dollar}-CH{dollar}sb2{dollar}CHCH{dollar}sb2{dollar}) as a precursor to (({dollar}rm Csb5Mesb5)sb2Lnrbracklbrack BPhsb4rbrack,{dollar} a general large scale route to ({dollar}rm Csb5Mesb5)sb2Ln(etasp3{dollar}-CH{dollar}sb2{dollar}CHCH{dollar}sb2{dollar}) was developed utilizing Ln(III) starting materials. Reactions between ({dollar}rm Csb5Mesb5)sb2LnClsb2K(TH