Syntheses and reactivity of cyclometalated iridium and ruthenium complexes

A series of mononuclear and dinuclear Ir(III) and Rh(III) cyclometalated complexes with dithiolate ligands have been synthesized. Treatment of [M(Buppy) 2(mu-Cl)]2 (M = Ir and Rh; BuppyH = 2-(4 '-tert-butylphenyl)pyridine) and [Ir(fppy) 2(mu-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{lcub}N(SPPh2)2{rcub}] and [Ir(fppy)2(S 2CNEt2)], respectively. Treatment of [M(ppy)2(OH 2)][OTf] (M = Ir and Rh; OTf = triflate) with K[SCN] gave [{lcub}M(Buppy) 2{rcub}2(mu-SCN)2] (M = Ir, Rh). Interaction of [M(Buppy) 2(mu-Cl)]2 (M = Ir and Rh) with [Et4N] 2[WQ4] (Q = S or Se) gave heterometallic complexes [{lcub}M(Buppy 2{rcub}2(mu-WQ4)]. Hydrolysis of [{lcub}Ir(Buppy) 2{rcub}2(WS4)] gave[{lcub}Ir(Buppy)2{rcub}2{lcub}W(O)(mu-S) 2(mu3-S){rcub}] 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{lcub}Ni(P1){rcub}] 2(mu-Cl)2 that reacted with Na[S2CNEt2 ] to give [Pd(S2CNEt2){lcub}Ni(P1){rcub}]. Reaction of [Ni(HP1)] with [Ir(H)2(PPh3) 2(Me2CO)2][BF4] afforded [Ir(H)Cl(PPh 3)2{lcub}Ni(P1){rcub}]. Treatment of [M(H4P)] (M = Ni(II) or Fe(III)Cl; P = tetrakis[4'-(2″ -pyridyl)phenyl]porphyrin) with [Cp*IrCl2]2 (Cp* = eta5-C5Me5) gave [M{lcub}P(IrCp*Cl){rcub}].; 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 6H8){lcub}(NCHppy)Pd(S2CNEt2){rcub}2] has been synthesized from [Pd(fppy)(S2CNEt2)] and ( R,R)-1,2-diaminocyclohexane. A bisphosphinite metalloligand [{lcub}Ir(ppy) 2{lcub}[OP(OEt)2]2H{rcub}] and its vanadium(IV) compound [{lcub}Ir(ppy)2[OP(OEt)2]2]2(VO){rcub}] 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-PhC6H 4, 2-thienyl and C6H4CH2OH) afforded [Ir(4-R-ppy)2(dtbpy)][OTf]. Treatment of 53 with B 2(pin)2 (pin = pinacolate) afforded [Ir{lcub}4-(pin)B-ppy{rcub} 2(dtbpy)][OTf]. The alkynyl complexes [Ir(4-Phppy)2(dtbpy)][OTf] and [Ir{lcub}4-Me2(OH)C≡C-ppy{rcub}(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)][OTf] with [P(O)(OEt2){lcub}CN2(COMe){rcub}] afforded [Ir{lcub}3-HC≡C-ppy{rcub}2(dtbpy)][OTf].; Some cyclometalated organo-ruthenium(II) complexes have been synthesized by transmetalation of Ru(II) chloride compounds with [Hg(mppy)(mu-Cl)] 2 (mppyH = 2-(p-tolyl)pyridine). Treatment of [Cp*RuCl2] x with [Hg(mppy)(mu-Cl)]2 afforded the dinuclear Ru(II)-Ru(IV) compound [Cp*Ru(mu-eta6,eta2-mppy)RuCl 2Cp*][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.