Please use this identifier to cite or link to this item: http://hdl.handle.net/1783.1/4007

Ruthenium and osmium complexes with sulfur- and selenium-donor ligands

Authors Lau, Kwok-Kin
Issue Date 2000
Summary A series of ruthenium complexes with dialkyldithiophosphate [PS2(RO)2-(where R = Et, i-Pr, tBu or PhCH2) were synthesized and characterized. The solid-state structures of cis-Ru(PPh3)2[PS2(EtO)2]2 and RuH(CO)(PPh3)2[PS2(EtO)2] have been determined and characterized by X-ray crystallography. Ruthenium η6-p-cymene complexes with imidodiphosphinosulfide [N(PPh2S)2]- and dialkyldithiophosphate ligands were also successfully synthesized. Treatment of [RuC1{N(PPh2S)2}(η6-p-cymene)]with two equivalents of [Ag(O3SCF3)] led to formation of Ru(III) complex [(η6-p-cymene)Ru{N(PPh2S)2}(SO3CF3)2].Reaction of [RuC12(CO)2]x with two equivalents of K[N(PiPr2S)2] and Na[HB(mt)3] (where mt = 2-sulfanyl-1-methylimidazole) in refluxing DMF resulted in formation of cis-Ru[N(PiPr2S)2]2(CO)2 and {HB(mt)3}RuC1(CO)2 respectively. The selenide analog Ru[N(PPh2Se)2]2(PPh3) was synthesized and structurally characterized by X-ray crystallography. The osmium(III) complexes Os[N(PPh2S)2]3 and OsCl2(PPh3)2[PS2(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(PR2Q)2]- (where R = Ph or i-Pr; Q = S or Se), dialkyldithiophosphate [PS2(RO)2]- (where R = Et, i-Pr or tBu) and 1,4,7-trithiacyclononane ([9]aneS3) were synthesized. The solid-state structures of Ru(=CHPh)[N(PPh2S)2]2 and Ru(=CHPh)[Ph2PNP(Se)Ph2]2 have been determined by X-ray crystallography. Treatment of Ru(=CHPh)[N(PPh2S)2]2 with CO afforded trans-Ru(CO)2[N(PPh2S)2]2. Moreover, Ru(=CHPh)[N(PPh2S)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(PPh2S)2]2,Ru(=CHOEt)[N(PPh2S)2]2 and Ru(=CHC3H3N2)[N(PPh2S)2]2 (where C3H3N2 = imidazole) respectively. Ru(=CHPh)[N(PPh2S)2]2,[[Kappa]2-([9]aneS3)Ru(=CHPh)(PCy3)Cl2 and Ru(=CHPh)[Ph2PNP(Se)Ph2]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 [Et4N]2[WSe4] with two equivalents of CuCl and two equivalents of PCy3 led to formation of orange [WSe4][Cu(PCy[subscrip 3])2][Cu(PCy3)] and red [WSe2(CH2Se2)]2[Cu(PCy3)]2.
Note Thesis (M.Phil.)--Hong Kong University of Science and Technology, 2000
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