THESIS
2016
xxi, 129 pages : illustrations ; 30 cm
Abstract
Selective H/D exchange reactions of olefins with D
2O using metal hydride were
developed. Heating a mixture of olefins and D
2O at 100 °C in the presence of 3 mol % of
OsHCl(CO)(PPh
3)
3 leads to the formation of deuterated olefins. The incorporation of
deuterium mainly occurs at the vinyl carbon and trace degree of deuteration is also found at
alkyl chain directly attached to the vinyl group.
An efficient and convenient one-pot direct H/D exchange reaction of aldehydes with D
2O
was developed. Heating a mixture of aldehydes and D
2O in the presence of 3 mol % of
MHCl(CO)(PPh
3)
3 (M = Ru, Os) leads to the formation of 1-deuterated aldehydes. The
incorporation of deuterium occurs only at the formyl carbon.
The synthesis and reactivities of ruthenium(II) complexes with readily a...[
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Selective H/D exchange reactions of olefins with D
2O using metal hydride were
developed. Heating a mixture of olefins and D
2O at 100 °C in the presence of 3 mol % of
OsHCl(CO)(PPh
3)
3 leads to the formation of deuterated olefins. The incorporation of
deuterium mainly occurs at the vinyl carbon and trace degree of deuteration is also found at
alkyl chain directly attached to the vinyl group.
An efficient and convenient one-pot direct H/D exchange reaction of aldehydes with D
2O
was developed. Heating a mixture of aldehydes and D
2O in the presence of 3 mol % of
MHCl(CO)(PPh
3)
3 (M = Ru, Os) leads to the formation of 1-deuterated aldehydes. The
incorporation of deuterium occurs only at the formyl carbon.
The synthesis and reactivities of ruthenium(II) complexes with readily available
secondary phosphine oxides were investigated. Catalytic hydration of phenylacetylene
mediated by such Ru(II) phosphino complexes was performed.
Reaction of a pyrrole-based (PNP)
-Tl
+ ligand ([PNP])
- = [2,5-(R
2PCH
2)
2C
4H
2N]
-) with
RuCl
2(PPh
3)
3 in THF produced the ruthenium(II) complex, Ru(PNP)Cl(PPh
3), which has been characterized by
1H,
31P{
1H} and
13C{
1H} NMR Spectroscopy. Treatment of (PNP)
-Li
+ with
RuHCl(CO)(PPh
3)
3 gave the 18e
- ruthenium(II) hydride complex RuH(CO)(PNP)(PPh
3).
Ru(PNP)Cl(PPh
3) was reacted with PMe
3 to give Ru(PNP)Cl(PMe
3)
2, although isolation of
such complex is so far unsuccessful. Reaction of Ru(PNP)Cl(PPh
3) with HC≡CPh gave
(PNP)RuCl(PPh
3)(=C=C(H)Ph) while reactions of Ru(PNP)Cl(PPh
3) with HC≡CC(OH)R’R”
were found to give vinylidene complexes, Ru(PNP)Cl(PPh
3)(=C=CHC(OH)R’R”).
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