Please use this identifier to cite or link to this item: http://hdl.handle.net/1783.1/5938

Synthesis and reactivity of iridium, rhodium and ruthenium alkyl complexes containing 2,2'-bipyridine

Authors Chan, Ka Wang
Issue Date 2008
Summary Heating [Rh(dtbpy)(CH2CMe2CC6H4)(Rh-CC)(CH2CMe2Ph)] (dtbpy = 4,4’-di-tert-butyl-2,2’-dipyridyl) at 138°C in xylene resulted in intra-molecular C-H activation of the neophyl group and the formation of [Rh(dtbpy)(CH2CMe2CC6H4)(Rh-CC)(C6H4-tBu-2)]. Refluxing [Ir(dtbpy)(CH2CMe2CC6H4)(Ir-CC)(C6H4-tBu-2)] with 2-phenylpyridine in toluene afforded [Ir(dtbpy)(CH2CMe2Ph)Cl(ppy)], which was deportonated by nBuLi to give the bis-cyclometalated compound [Ir(dtbpy)(CH2CMe2CC6H4)(Ir-CC)(ppy)]. Reaction of [Ir(dtbpy)(CH2CMe2CC6H4)(Ir-CC)(C6H4-tBu-2)] with 4-(2-pyridyl)benzaldehyde or benzaldehyde led to decarbonylation of the formyl group and afforded [Ir(dtbpy)(CH2CCMe2Ph)(Ir-C)(CO)(R)] (R = 4-(2’-pyridyl)phenyl, phenyl). Treatment of [M(dtbpy)(CH2CMe2Ph)(OTs)2(H2O)] (M = Rh, Ir) with Na[BArF4] afforded [{M(dtbpy)(CH2CMe2Ph)(OTs)(H2O)}2(μ-OTs)2]2[BArF4]2 (M = Rh, Ir), which can catalyze H/D exchange of THF with D2O. Transmetalation of [Ru(dtbpy)(NO)Cl3] with Me3CCH2Li and Me3SiCH2MgCl afforded the trialkyl compounds [Ru(dtbpy)(NO)(R)3] (R = CH2CMe3, CH2SiMe3). Protonation of [Ru(dtbpy)(NO)(R)3] with HCl afforded [Ru(dtbpy)(NO)(R)2Cl] (R = CH2CMe3, CH2SiMe3). Chloride abstraction of [Ru(dtbpy)(NO)(CH2CMe3)2Cl] with silver triflate (AgOTf) afforded [Ru(dtbpy)(NO)(CH2SiMe3)2(OTf)], which reacted with NH2R to yield amine adducts [Ru(dtbpy)(NO)(CH2SiMe3)2(NH2R)][OTf] (R = tBu, mes, p-tol). [Ru(dtbpy)(NO)(CH2SiMe3)2(OTf)] reacted with sodium phenoxide, siloxides and thiolates to afford [Ru(dtbpy)(NO)(CH2SiMe3)2(OR)] (R = Ph, SiMe3, SiPh3, Si(OtBu)3) and [Ru(dtbpy)(NO)(CH2SiMe3)2(SR)] (R = xyl, SiPh3) (xyl = 2,6-dimethylphenyl), respectively. Treatment of [Ru(dtbpy)(NO)(CH2SiMe3)2(OTf)] with KOAc and K[NOsO3] gave [Ru(dtbpy)(NO)(CH2SiMe3)2(OAc)] and dimetallic [Ru(dtbpy)(NO)(CH2SiMe3)2(NOsO3)] respectively. Treatment of [Ru(dtbpy)(NO)(CH2SiMe3)3] with SBA-15 resulted in elimination of one equivalent of SiMe4. Spectroscopic data suggested that the Ru-grafted species was the alkyl species [Ru(dtbpy)(NO)(CH2SiMe3)2(SBA-15)]. Treatment of [Ru(L)(NO)Cl3] (L = bpy, 2 tBupy) with NaSC6F4H afforded the photolabile nitrosyl thiolate compounds [Ru(L2)(NO)(SC6F4H)3] (L2 = bpy, 2tBupy). Reaction of Ru(NO)Cl3⋅H2O with NaSC6F4H and Na(S-tBu) yielded the dimer [{Ru(NO)(SC6HF4)2}2(μ-O)(μ-SC6HF4)2Na] and trimer [{Ru(NO)(S-tBu)}3(μ2-S-tBu)3(μ3-O)(μ3-S)Na] respectively. Treatment of M(P) (M = H2, Mn, Co, Ni; P2- = tetrakis[4’-(2”-pyridyl)phenyl]porphyrin dianion) with [Cp*IrCl2]2 (Cp* = η5-C5Me5) and NaOAc afforded the cyclometalated compounds [M{P(Cp*IrCl)4}] (M = H2, Mn, Co, Ni). Treatment of M(P) (M = Co, Ni) with [(η6-arene)RuCl2]2 (arene = p-cymene, C6H6) and NaOAc afforded the bimetallic porphyrins [M{P((η6-arene)RuCl)4}] (M = Co, Ni; arene = C6H6, p-cymene).
Note Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2008
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