Abstract
A series of mononuclear and dinuclear Ir(III) and Rh(III) cyclometalated complexes with dithiolate ligands have been synthesized. Treatment of [M(Buppy)2(μ-Cl)]2(M = Ir and Rh; BuppyH = 2-(4'-tert-butylphenyl)pyridine) and [Ir(fppy)2(μ-Cl)]2 (fppyH = 4-(2-pyridyl)benzaldehyde) with [S^S]- ligands afforded monomeric [Rh(Buppy)2(S^S)] (S^S = S2P(OMe)2, N(SPPh2)2), [Ir(Buppy)2{N(SPPh2)2}] and [Ir(fppy)2(S2CNEt2)], respectively. Treatment of [M(ppy)2(OH2)][OTf] (M = Ir and Rh; OTf = triflate) with K[SCN] gave [{M(Buppy)2}2(μ-SCN)2] (M = Ir, Rh). Interaction of [M(Buppy)2(μ-Cl)]2 (M = Ir and Rh) with [Et4N]2 [WQ4] (Q = S or Se) gave heterometallic complexes [{M(Buppy)2}2(μ-WQ4)]. Hydrolysis of [{Ir(Buppy)2}2{(WS4)] gave[{Ir(Buppy)2}2{W(O)(μ-S)2(μ3-S)}] that has been characterized by X-ray diffraction.2-Phenylpyridine (ppy) substituted porphyrins have been synthesized. Treatment of [Ni(HP1)] (H3P1= meso-5- [4'-(2"-pyridyl)phenyl]-10,15,20-triphenyporphyrin) with K2[PdCl4] afforded [ Pd{Ni(P1)}]2(μ-Cl)2 that reacted with Na[S2CNEt2] to give [Pd(S2CNEt2) {Ni(P1)}]. Reaction of [Ni(HP1)] with [Ir(H)2(PPh3)2(Me2CO)2] [BF4] afforded [Ir(H)Cl(PPh3)2{Ni(P1)}]. Treatment of [M(H4P)] (M = Ni(II) or Fe(III)Cl; P = tetrakis [4'-(2"-pyridyl)phenyl] porphyrin) with [Cp*IrCl2]2 (Cp* =η5-C5Me5) gave [M{P(IrCp*Cl)}].
Schiff base metalloligands containing the [Ir(ppy)2]+ moiety have been synthesized by reactions of [Ir(fppy)2(S2CNEt)] with 2-amino-4-tert-butyl-phenol, 2-aminothiophenol and 2-aminomethylpyridine. In addition, the chiral metalloligand [(C6H8) {(NCHppy)Pd(S2CNEt2)}2] has been synthesized from [Pd(fppy)(S2CNEt2)] and (R,R)-1,2-diaminocyclohexane. A bisphosphinite metalloligand [{Ir(ppy)2{[OP(OEt)2]2H}] and its vanadium(IV) compound [{Ir(ppy)2[OP(OEt)2]2}2(VO)} were synthesized.
Pd-catalyzed cross-coupling of [Ir(4-Br-ppy)2(dtbpy)][OTf] (53) (dtbpy = 4,4'-di-tert-butyl-2,2'-bipyridine) with RB(OH)2 (R = 4-PhC6H4, 2-thienyl and C6H4CH2OH) afforded [Ir(4-R-ppy)2(dtbpy)] [OTf]. Treatment of 53 with B2(pin)2 (pin = pinacolate) afforded [Ir{4-(pin)B-ppy}2(dtbpy)][OTf]. The alkynyl complexes [Ir(4-Phppy)2(dtbpy)][OTf] and [Ir{4-Me2(OH)C≡C-ppy}(4-Br-ppy)(dtbpy)][OTf] were prepared by cross-coupling of 53 with PhC≡CSnMe3 and Me2C(OH)C≡CH, respectively. Ohira's ethynylation of [Ir(fppy)2(dtbpy)] [OTfl with [P(O)(OEt2) {CN2(COMe)}] afforded [Ir {3-HC≡C-ppy}2(dtbpy)] [OTf].
Some cyclometalated organo-ruthenium(II) complexes have been synthesized by transmetalation of Ru(II) chloride compounds with [Hg(mppy)(μ-Cl)]2 (mppyH = 2-(p-tolyl)pyridine). Treatment of [Cp*RuCl2]x with [Hg(mppy)(μ-Cl)]2 afforded the dinuclear Ru(II)-Ru(IV) compound [Cp*Ru(μ-η6, η2-mppy)RuCl2Cp*] [Hg2Cl6]. Photo-substitution of cis-[Ru(bq)2(CO)2] (bqH = benzo[h]quinoline) with L (L = MeCN, PPh3 and py) afforded [Ru(bq)2(CO)(L)]. [RU(bq)2(CO)(MeCN)] is capable of catalyzing cyclopropanation of styrene with ethyl diazoacetate.
| Date of Award | 2005 |
|---|---|
| Original language | English |
| Awarding Institution |
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