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Please use this identifier to cite or link to this item: http://hdl.handle.net/1783.1/2685
Title: Synthesis and reactivity of 2,2'-bipyridine-supported iridium alkyl compounds : Metal complexes with chiral phosphine oxide and sulfoxide ligands
Other Titles: Metal complexes with chiral phosphine oxide and sulfoxide ligands
Authors: Sau, Yiu Keung
Issue Date: 2005
Abstract: Treatment of [Ir(dtbpy)Cl3(DMF)] (DMF = N,N-dimethylformamide; dtbpy = 4,4'-di-tert-2,2'-dipyridyl) with Me3SiCH2MgCl afforded the Ir(IIl) silyl complex [Ir(dtbpy)(SiMe3)Me(CH2SiMe3)], which reacted with t-BuNC and PhC≡CH to give [Ir(dtbpy)(SiMe3)Me(CH2SiMe3)(t-BuNC)] and [Ir(dtbpy)(SiMe3)(C≡CPh)(μ-C≡CPh)]2, respectively. Treatment of [Ir(dtbpy)Cl3(DMF)] with PhMe2CCH2MgCl afforded cyclometalated [Ir(dtbpy)(C6H4CMe3-2)(CH2CMe2C6H4)] that exhibits an Ir-HC agostic interaction between the Ir center and a tert-butyl C-H group. Treatment of [Ir(dtbpy)(C6H4CMe3-2)(CH2CMe2C6H4)] with NOBF4, tetracyanoethylene and pyridinium tribromide afforded [Ir(dtbpy)(C6H3CMe3-2-NO2-4)(CH2CMe2C6H3NO2-4], [Ir(dtbpy)(C6H4CMe3-2)(CH2CMe2C6H3{C2(CN)3}-4)] and [Ir(dtbpy)(C6H4CMe3-2)(CH2CMe2C6H3Br-4)]. Treatment of [Ir(dtbpy)(C6H4CMe3-2)(CH2CMe2C6H4)] with diethyl meleate led to isolation of the iridafuran [Ir(dtbpy){k2(C,O)-C(CO2Et)=CHC(OEt)=O} (CH2CMe2C6H4)]. Oxidation of [Ir(dtbpy)(CH2CMe2C6H4)( μ-tolS)]2 and [Ir(dtbpy)(CH2CMe2Ph)(tdt)] (tdt = toluene-3,4-dithiolato) afforded the mixed-valence Ir(IIl)-Ir(lV) [Ir(dtbpy)(CH2CMe2C6H4)(μ-tolS)]2[BF4] and the Ir(lV)-Ir(lV) [Ir(dtbpy)(CH2CMe2Ph)(tdt)][BF4]2 compounds, respectively. Treatment of [Ir(dtbpy)Cl3(DMF)] with (p-xyl)MgBr (xyl = dimethylphenyl) afforded the Ir(IIl) tri-aryl complex [Ir(dtbpy)(p-xyl)3]. Oxidation of [Ir(dtbpy)(p-xyl)3] with AgOTf in THF afforded the ID polymer [Ir(dtbpy)(p-xyl)3(AgOTf)3]n. Alkylation of [Ir(dtbpy)Cl3(DMF)] with ArfMgBr (Arf = 3,5-bis(trifluoromethyl)phenyl) afforded [Ir(dtbpy)(Arf)(DMF)(Cl0.7Br0.3)2] that reacted with o-xylNC to give [Ir(dtbpy)(Arf)(o-xylNC)(Cl0.7Br0.3)2]. [Cp*Ir(III)(ppy)(H2O)]+ (Hppy = 2-phenylpyridine) can catalyze oxidation and aziridination of styrene with PhIO and PhINTs (Ts = tosyl), respectively. Treatment of [Cp*Ir(III)(ppy)(NCMe)]+ with PhI=NTs led to insertion of the NTs group into the Ir-C(ppy) bond and the formation of [Cp*Ir(III)(TsN-ppy)(NCMe)]+. Treatment of [Cp*Ir(III)(ppy)(NCMe)]+ with phenylacetylene, 3-butyn-1-o1 and 2-phenyl-but-3-yn-2-o1 led to migratory insertion of the vinylidene and allenyldiene into the Ir-C(ppy) bond and the formation of [Cp*Ir{(Ph)(H)C-η3-CC(Ph)C(H)-ppy}]+, [Cp*Ir{η3-H2CC(H)C-C(H)-ppy}]+ and [Cp*Ir{(C6H4)(H2C)C-η2-C(H)C(H)-ppy}] +, respectively. Treatment of [Cp*Ir(III)(ppy)(H2O)]+ with RE-ER afforded the adducts [Cp*Ir(ppy)(η1-RE-ER)]+(E = S, Se and Te, R = tol and Ph), which reacted with Ag(OTf) gave [Cp*Ir(RE-ppy)(H2O)]2+. Treatment of (Sp)-tBuPhP(O)H (HL1) with PdCl2(MeCN)2 afforded [Pd{(L1)2H}]2(μ-Cl)2. X-ray crystallography established that HL1 binds to Pd(ll) with the retention of configuration at phosphorus. Treatment of [Pd{(L1)2H}]2(μ-Cl)2 with Na[S2CNEt2] gave Pd[(L1)2H](S2CNEt2), which reacted with V(O)(acac)2 (acac = acetylacetone) and Cu(NO3)2 to give V(O)[Pd(L1)2(S2CNEt2)]2 and Cu[Pd(L1)2(S2CNEt2)]2, respectively. Chiral tetradentate sulfoxide-containing Schiff base ligands, N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]ethylenediamine (L2),(1R,2R)-N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanedimine ((R,R)-L3), and (1S,2S)-N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanedimine ((S,S)-L3) have been synthesized. Treatment of [Ru(PPh3)3Cl2] with L afforded trans-[Ru(L)Cl2] (L = L2, (R,R)-L3 and (S,S)-L3), respectively. The configuration and S-bonding mode of the tetradentate sulfoxide ligands in these complexes have been unambiguously established by X-ray crystallography. Tridentate N, N-bis[2-(S)-(p-tolylsulfinyl)benzyl]methylamine (L4) and 1,5-bis[(S)-(p-tolylsulfinyl)methyl]benzene (L5) have been synthesized. Treatment of [Pd(NCMe)4]2+ with L4 afforded [Pd(L4)(NCMe)]2+.
Description: Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2005
xxxvii, 316 leaves : ill. ; 30 cm
HKUST Call Number: Thesis CHEM 2005 Sau
URI: http://hdl.handle.net/1783.1/2685
Appears in Collections:CHEM Doctoral Theses

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