LEADER 00000nam  2200433   4500 
001    AAI3359392 
005    20100830094244.5 
008    100830s2009    ||||||||||||||||| ||eng d 
020    9781109201895 
035    (UMI)AAI3359392 
040    UMI|cUMI 
100 1  Khusnutdinova, Julia 
245 10 Ligand-enabled platinum-carbon bond functionalization 
       utilizing dioxygen as the terminal oxidant 
300    383 p 
500    Source: Dissertation Abstracts International, Volume: 70-
       06, Section: B, page: 3502 
500    Adviser: Andrei N. Vedernikov 
502    Thesis (Ph.D.)--University of Maryland, College Park, 2009
520    The use of organotransition metal complexes for selective 
       functionalization of hydrocarbons is of great importance. 
       Dioxygen is the most practical oxidant for large-scale 
       applications in the petroleum industry. The focus of this 
       work is the development of ligand-modulated platinum-based
       systems that can utilize O2 or air for selective 
       transformation of organoplatinum(II) derivatives into 
       alcohols, diols, aminoalcohols and epoxides in aqueous 
       media 
520    We found that the hemilabile tripod ligand 
       dipyridylmethanesulfonate (dpms) enables facile aerobic 
       functionalization of various PtIIMe complexes and some 
       olefin hydroxo PtII complexes in hydroxylic solvents such 
       as water and alcohols 
520    Complexes LPtII(R)(HX) (L = dpms; R = Me, Ph; HX = H 2O, 
       MeOH, PhNH2) are oxidized by O2 to yield virtually 
       quantitatively LPtIV(R)(X)(OH). Some of the derived Pt IV 
       alkyls LPtIV(Alk)(X)(OH) (X = OH, OMe) can reductively 
       eliminate methanol in high yield. The mechanism of C-O 
       elimination from LPt IV(Me)(X)(OH) (X = OH, OMe) in acidic
       aqueous media involves two concurrent pathways: an SN2 
       attack by water and an SN2 attack by a hydroxo or methoxo 
       ligand of another PtIV species. In the latter case 
       dimethyl ether is produced 
520    The complex (dpms)Pt(ethylene)(OH) is oxidized by O2 in 
       water to give a PtIV hydroxyethyl derivative that 
       reductively eliminates ethylene oxide and ethylene glycol 
       in aqueous solutions 
520    The complexes derived from cyclic alkenes, cis-cyclooctene,
       norbornene, benzonorbornadiene, (dpms)PtII(cy-alkene)(OH),
       undergo olefin oxoplatination to give 1,2-
       oxaplatinacyclobutanes (Pt II oxetanes). The derived PtII 
       oxetanes are easily oxidized by O2 to produce PtIV 
       oxetanes. The latter eliminate cleanly the corresponding 
       epoxides by the mechanism of direct C( sp3)-O reductive 
       eliminations, unprecedented in organoplatinum chemistry 
520    The 1,2-azaplatinacyclobutanes (PtII azetidines) LPt 
       II(CH2CH2NHR-kappaC,kappaN) (R = t-Bu, Me) are oxidized by
       O2 in the presence of acids to give PtIV azetidine 
       complexes, [LPt(CH2CH 2NHR-kappaC,kappaN)(OH)]+. The 
       latter undergo reductive elimination of N-alkyl 
       ethanolammonium salts, HOCH2CH2NH2R+, in acidic aqueous 
       solutions at elevated temperatures 
520    Efficient catalytic systems based on palladium acetate, 
       di(6-pyridyl)ketone and 6-methyldi(2-
       pyridyl)methanesulfonate ligands, suitable for selective 
       oxidation of ethylene with H2O2 to glycol acetates were 
       developed. Glycol acetates were obtained in high 
       selectivity and high yield on H2O2 under mild reaction 
       conditions 
590    School code: 0117 
650  4 Chemistry, Inorganic 
690    0488 
710 2  University of Maryland, College Park.|bChemistry 
773 0  |tDissertation Abstracts International|g70-06B 
856 40 |uhttp://pqdd.sinica.edu.tw/twdaoapp/servlet/
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