THESIS
2000
xxv, 179 leaves : ill. ; 30 cm
Abstract
A series of ruthenium complexes with dialkyldithiophosphate [PS
2(RO)
2-(where R = Et, i-Pr,
tBu or PhCH
2) were synthesized and characterized. The solid-state structures of cis-Ru(PPh
3)
2[PS
2(EtO)
2]
2 and RuH(CO)(PPh
3)
2[PS
2(EtO)
2] have been determined and characterized by X-ray crystallography. Ruthenium η
6-p-cymene complexes with imidodiphosphinosulfide [N(PPh
2S)
2]
- and dialkyldithiophosphate ligands were also successfully synthesized. Treatment of [RuC1{N(PPh
2S)
2}(η
6-p-cymene)]with two equivalents of [Ag(O
3SCF
3)] led to formation of Ru(III) complex [(η
6-p-cymene)Ru{N(PPh
2S)
2}(SO
3CF
3)
2].Reaction of [RuC1
2(CO)
2]
x with two equivalents of K[N(P
iPr
2S)
2] and Na[HB(mt)
3] (where mt = 2-sulfanyl-1-methylimidazole) in refluxing DMF resulted in formation of cis-Ru[N(P
iPr
2S)
2]
2(CO)
2 and {HB(mt)
3}RuC1...[
Read more ]
A series of ruthenium complexes with dialkyldithiophosphate [PS
2(RO)
2-(where R = Et, i-Pr,
tBu or PhCH
2) were synthesized and characterized. The solid-state structures of cis-Ru(PPh
3)
2[PS
2(EtO)
2]
2 and RuH(CO)(PPh
3)
2[PS
2(EtO)
2] have been determined and characterized by X-ray crystallography. Ruthenium η
6-p-cymene complexes with imidodiphosphinosulfide [N(PPh
2S)
2]
- and dialkyldithiophosphate ligands were also successfully synthesized. Treatment of [RuC1{N(PPh
2S)
2}(η
6-p-cymene)]with two equivalents of [Ag(O
3SCF
3)] led to formation of Ru(III) complex [(η
6-p-cymene)Ru{N(PPh
2S)
2}(SO
3CF
3)
2].Reaction of [RuC1
2(CO)
2]
x with two equivalents of K[N(P
iPr
2S)
2] and Na[HB(mt)
3] (where mt = 2-sulfanyl-1-methylimidazole) in refluxing DMF resulted in formation of cis-Ru[N(P
iPr
2S)
2]
2(CO)
2 and {HB(mt)
3}RuC1(CO)
2 respectively. The selenide analog Ru[N(PPh
2Se)
2]
2(PPh
3) was synthesized and structurally characterized by X-ray crystallography. The osmium(III) complexes Os[N(PPh
2S)
2]
3 and OsCl
2(PPh
3)
2[PS
2(
iPrO)
2] were synthesized and their structures have been established by X-ray crystallography.
A series of novel ruthenium benzylidene complexes with sulfur- and selenium-donor ligands, namely imidodiphosphinochalcogenide [N(PR
2Q)
2]
- (where R = Ph or i-Pr; Q = S or Se), dialkyldithiophosphate [PS
2(RO)
2]
- (where R = Et, i-Pr or
tBu) and 1,4,7-trithiacyclononane ([9]aneS
3) were synthesized. The solid-state structures of Ru(=CHPh)[N(PPh
2S)
2]
2 and Ru(=CHPh)[Ph
2PNP(Se)Ph
2]
2 have been determined by X-ray crystallography. Treatment of Ru(=CHPh)[N(PPh
2S)
2]
2 with CO afforded trans-Ru(CO)
2[N(PPh
2S)
2]
2. Moreover, Ru(=CHPh)[N(PPh
2S)
2]
2 was proved to be capable of undergoing metathesis reactions with acyclic olefins such as 1-hexene, ethyl vinyl ether and 1-vinylimidazole to give Ru(=CH-n-Bu)[N(PPh
2S)
2]
2,Ru(=CHOEt)[N(PPh
2S)
2]
2 and Ru(=CHC
3H
3N
2)[N(PPh
2S)
2]
2 (where C
3H
3N
2 = imidazole) respectively. Ru(=CHPh)[N(PPh
2S)
2]
2,[[Kappa]
2-([9]aneS
3)Ru(=CHPh)(PCy
3)Cl
2 and Ru(=CHPh)[Ph
2PNP(Se)Ph
2]
2 were found to be active catalysts for polymerization of norbornene. Ruthenium alkenylidene and allenylidene complexes with above sulfur-containing ligands were also synthesized.
Treatment of [Et
4N]
2[WSe
4] with two equivalents of CuCl and two equivalents of PCy
3 led to formation of orange [WSe
4][Cu(PCy[subscrip 3])
2][Cu(PCy
3)] and red [WSe
2(CH
2Se
2)]
2[Cu(PCy
3)]
2.
Post a Comment