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 = S
2P(OMe)
2, N(SPPh
2)
2), [Ir(Buppy)
2{N(SPPh
2)
2}] and [Ir(fppy)
2(S
2CNEt
2)], respectively. Treatment of [M(ppy)
2(OH
2)][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 [Et
4N]
2 [WQ
4] (Q = S or Se) gave heterometallic complexes [{M(Buppy)
2}
2(μ-WQ
4)]. Hydrolysis of [{Ir(Buppy)
2}
2{(WS
4)] gave[{Ir(Buppy)
2}
2{W(O)(μ-S)
2(μ
3-S)}] that has been characterized by X-ray di...[
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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 = S
2P(OMe)
2, N(SPPh
2)
2), [Ir(Buppy)
2{N(SPPh
2)
2}] and [Ir(fppy)
2(S
2CNEt
2)], respectively. Treatment of [M(ppy)
2(OH
2)][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 [Et
4N]
2 [WQ
4] (Q = S or Se) gave heterometallic complexes [{M(Buppy)
2}
2(μ-WQ
4)]. Hydrolysis of [{Ir(Buppy)
2}
2{(WS
4)] gave[{Ir(Buppy)
2}
2{W(O)(μ-S)
2(μ
3-S)}] that has been characterized by X-ray diffraction.
2-Phenylpyridine (ppy) substituted porphyrins have been synthesized. Treatment of [Ni(HP
1)] (H
3P
1= meso-5- [4'-(2"-pyridyl)phenyl]-10,15,20-triphenyporphyrin) with K
2[PdCl
4] afforded [ Pd{Ni(P
1)}]
2(μ-Cl)
2 that reacted with Na[S
2CNEt
2] to give [Pd(S
2CNEt
2) {Ni(P
1)}]. Reaction of [Ni(HP
1)] with [Ir(H)
2(PPh
3)
2(Me
2CO)
2] [BF
4] afforded [Ir(H)Cl(PPh
3)
2{Ni(P
1)}]. Treatment of [M(H
4P)] (M = Ni(II) or Fe(III)Cl; P = tetrakis [4'-(2"-pyridyl)phenyl] porphyrin) with [Cp*IrCl
2]
2 (Cp* =η
5-C
5Me
5) gave [M{P(IrCp*Cl)}].
Schiff base metalloligands containing the [Ir(ppy)
2]
+ moiety have been synthesized by reactions of [Ir(fppy)
2(S
2CNEt)] with 2-amino-4-tert-butyl-phenol, 2-aminothiophenol and 2-aminomethylpyridine. In addition, the chiral metalloligand [(C
6H
8) {(NCHppy)Pd(S
2CNEt
2)}
2] has been synthesized from [Pd(fppy)(S
2CNEt
2)] 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-PhC
6H
4, 2-thienyl and C
6H
4CH
2OH) afforded [Ir(4-R-ppy)
2(dtbpy)] [OTf]. Treatment of 53 with B
2(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-Me
2(OH)C≡C-ppy}(4-Br-ppy)(dtbpy)][OTf] were prepared by cross-coupling of 53 with PhC≡CSnMe
3 and Me
2C(OH)C≡CH, respectively. Ohira's ethynylation of [Ir(fppy)
2(dtbpy)] [OTfl with [P(O)(OEt
2) {CN
2(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*RuCl
2]
x with [Hg(mppy)(μ-Cl)]
2 afforded the dinuclear Ru(II)-Ru(IV) compound [Cp*Ru(μ-η
6, η
2-mppy)RuCl
2Cp*] [Hg
2Cl
6]. Photo-substitution of cis-[Ru(bq)
2(CO)
2] (bqH = benzo[h]quinoline) with L (L = MeCN, PPh
3 and py) afforded [Ru(bq)
2(CO)(L)]. [RU(bq)
2(CO)(MeCN)] is capable of catalyzing cyclopropanation of styrene with ethyl diazoacetate.
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