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Part I Ruthenium complexes with an oxygen tripodal ligand ; Part II Metal complexes with functionalized cyclometalated ligands

Ruthenium complexes with an oxygen tripodal ligand

Metal complexes with functionalized cyclometalated ligands

Authors Lai, Chun Sing
Issue Date 2010
Summary Treatment of Ru(H)Cl(CO)(PPh3)3 and Ru(H)Cl(CO)(PCy3)2 (Cy = cyclohexyl) with NaLOEt (LOEt- = [(η5-C5H5)Co{P(O)(OEt)2}3]-) afforded LOEt(CO)(PR3)RuH (R = Ph (1) and Cy (2)), which have been characterized by X-ray crystallography. It was found that the use of recrystallized samples of the Ru hydridesas starting materials and removal of the phosphines from the crude products with hexane are critical for the synthesis of complexes 1 and 2 in pure form. The protonation of 1 with HBF4 in CD2Cl2 at low temperature resulted in appearance of new 1H NMR signals at δ 11.78, -12.52 and -17.61 ppm, which can be assigned to Ru hydride species. The protonation of 1 with HCl in Et2O afforded LOEt(CO)(PR3)RuCl. The reactions between 1 and RSO2N3 yielded the (arylsulfonyl)amido complexes LOEt(CO)(PPh3)Ru(NHSO2R) (R = 2,4,6-i-Pr3C6H3 (3), 4-t-BuC6H4 (4), 4-MeC6H4 (5)). The crystal structure of 3 has been determined. The photolysis of 5 resulted in the complex LOEt(MeCN)(PPh3)Ru(NHSO2C6H4Me-4). Treatment of Ru(PCy3)2(Cl)2(=CHPh) with NaLOEt afforded LOEtRu(PCy3)(Cl)(=CHPh) which can catalyze the ring-closing metathesis of diethyl 1,2-diallylmalonate. The reaction between (Et4N)2MoS4 and NaLOEt yielded the dinuclear Mo(V) sulfido complex [LOEtMo(O)(μ-S)]2 characterized by X-ray crystallography. Four functionalized N^C ligands, 3-(pyridin-2-yl)phenol (HL1), diethyl hydroxy(4-(pyridin-2-yl)phenyl)ethylphosphonate (HL2), 2-(thiophen-3-yl)pyridine (HL3), and hydroxy(4-(pyridin-2-yl)phenyl)methylphosphonic acid (HL4), have been synthesized. Refluxing IrCl3 with HL1 in methoxyethanol/H2O gives [Ir(L1)2Cl]2. Treatment of [Ir(L1)2Cl]2 with 3 equivalents of silver triflate (AgOTf) yielded [Ir(L1)2(dtbpy){Ag(MeCN)2}](OTf)2. The crystal structure of [Ir(L1)2(dtbpy){Ag(MeCN)2}](OTf)2 shows that there is an interaction between the [Ag(MeCN)2]+ moiety and the ipso carbons of the two L1 ligands. Reaction of [Ir(η5-C5Me5)Cl2]2 with HL2 in the presence of NaOAc resulted in the formation of Ir(η5-C5Me5)(L2)Cl. Reaction between LiL3 and [Ir(COD)Cl]2 yielded [Ir(COD)(L3)] (COD = 1,4-cyclooctadiene) that underwent oxidative addition with MeI to give [Ir(COD)(L3)(CH3)(I)]. The reaction between [Ru(η6-p-cymene)Cl2]2 and HL2 in the presence of NaOAc yielded Ru(η6-p-cymene)(L2)(Cl).
Note Thesis (M.Phil.)--Hong Kong University of Science and Technology, 2010
Language English
Format Thesis
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