The first allylphosphane iridium complexes [IrCl2(η5-C5Me5)­{κ­(P)-R2PCH2CHCH2}] (R = iPr (1a), Ph (1b)) have been synthesized by the reaction of the dimeric complex [IrCl­(μ-Cl)­(η5-C5Me5)]2 with allyldiisopropylphosphane (ADIP) and allyldiphenylphosphane (ADPP), respectively. The cationic complex [IrCl­(η5-C5Me5)­{κ3(P,C,C)-iPr2PCH2CHCH2}]+ (3 + ) has been prepared by the reaction of complex 1a with NaX (X = BPh4, PF6) in dichloromethane. The complex 3+ reacts with phosphanes and alkanethiolates to give the uncommon cationic complexes [IrCl­(η5-C5Me5)­{κ2(P,C)-iPr2PCH2CH­(PR2R′)­CH2}]+ (5 + –7 +) and IrCl­(η5-C5Me5)­{κ3(P,C,S)-iPr2PCH2CH­(SR)­CH2}]+ (13 + and 14 + ) by chemo- and regioselective addition of the nucleophiles to the π-olefin system. The reaction of 1a with LiBHEt3 gives the neutral complex [IrCl­(η5-C5Me5)­{κ2(P,C)-iPr2PCH2CH2CH2}] (10). For comparative purposes, the synthesis of the complex [RhCl­(η5-C5Me5)­{κ3(P,C,C)-iPr2PCH2CHCH2}]+ (4 + ) and its reactivity with phosphanes, hydride, and thiolates has been also assayed.

We have developed a chiral phosphoric acid-catalyzed enantioselective Friedel–Crafts alkylation reaction between pyrroles and indolylmethanols. Wide substrate scope was observed, and a chiral all-carbon quaternary center was constructed at the 3 position of indoles in high yields with high to excellent enantioselectivities (up to 99% ee).

The reactivity of the complexes [RhCl 2 (h 5 -C 5 Me 5 ){k(P)-Ph 2 P(CH 2 ) 2 CH=CH 2 }] (1), [MCl 2 (h 5 -C 5 Me 5 ){k(P)-R 2 PCH 2 CH=CH 2 }] (M = Rh, R = Ph (3 a), iPr (3 b); M = Ir, R = Ph (4 a), iPr (4 b)) towards various nucleophilic reagents (carbon-donor, nitrogen-donor and phosphorus-donor) in the presence of a halogen abstractor has been studied. The rhodium e iridium complexes undergo metal coordination of the ligand (L = CNR, CO, Py, P(OPh) 3 ) to give the new cationic complexes [MCl(h 5 -C 5 Me 5 )(L){k(P)-R 2 P(CH 2 ) n CH= CH 2 }][BPh 4 ] (M= Rh, Ir; L = CNR, CO, Py, P(OPh) 3 ) (5-19 a,b). However, the reaction with phosphanes follows a different way depending on the metal. While the rhodium complexes 3 a,b give the expected products [RhCl(h 5 -C 5 Me 5 )(L){k(P)-R 2 PCH 2 CH= CH 2 }][BPh 4 ] (20 a,b, 21 a and 22 a), the iridium complex 4 a suffer addition of the phosphane to the C=C affording the complexes [IrCl(h 5 -C 5 Me 5 ){k 2 (P,C)-Ph 2 PCH 2 CH(PR 'Ph 2 )CH 2 }][BPh 4 ] (R ' = Me (23 a), Ph (24 a)).

The diazido complexes [Ir(η 5 -C 5 Me 5 )(N 3 ) 2 -(PPh 3 )] (1a), [Ir(η 5 -C 5 Me 5 )(N 3 ) 2 {κ(P)-R 2 PCH 2 CH CH 2 }] (R = Ph (1b), i Pr (1c)) have been synthesized and their [3+2] cycloaddition reaction toward tetracyanoethylene and fumaronitrile investigated. Complexes 1a−1c react with tetracyanoethylene, giving single (2a, 2b, 2c) or double (4a, 4b) azide-nitrile cycloadducts. The complexes [Ir(η 5 -C 5 Me 5 )-have been obtained through the [3+2] cycloaddition reaction involving the azide ligands of complexes 1a,b and two geminal nitrile groups of tetracyanoethylene. Uncommon triazolinato stable complexes [Ir(η 5 -C 5 Me 5 )(N 3 )-{κ(N 1 )-N 3 CH(CN)CH(CN)}(PPh 3 )] (5a) and [Ir(η 5 -C 5 Me 5 )(N 3 ){κ(N 1 )-N 3 CH(CN)CH(CN)}{κ(P)-Ph 2 PCH 2 CHCH 2 }] (5b) have been stereoselectively prepared from 1a,b and fumaronitrile through a single [3+2] cycloaddition reaction between the CC double bond of fumaronitrile and an azide ligand. The treatment of a dichloromethane solution of complexes 5a and 5b with basic alumina gives regioselectively the triazolato complexes 6a and 6b. The structures of complexes 2b, 3a, and 6a have been determined by single-crystal X-ray diffraction analysis.

Dialkynyl iridium(III) complexes [Ir(η 5 -C 5 Me 5 )(C CPh) 2 (PPh 2 R)] (R = Ph (2a), Me (2b), CH 2 CHCH 2 (2c)) have been prepared by reaction of the complexes [Ir(η 5 -C 5 Me 5 )Cl 2 (PPh 2 R)] (R = Ph (1a), Me (1b), CH 2 CHCH 2 (1c)) and lithium phenylacetylide. Alternatively, complexes 2a,b have been synthesized by the treatment of the complexes [Ir(η 5 -C 5 Me 5 )I 2 (PPh 2 R)] (R = Ph (3a), Me (3b)) with [AgCCPh] n . The reactivity of the complex [Ir(η 5 -C 5 Me 5 )(CCPh) 2 (PPh 3 )] (2a) toward electrophiles is reported. Thus, complex 2a reacts with tetrafluoroboric acid to give the new butenynyl complex [Ir(η 5 -C 5 Me 5 ){η 3 -C(Ph)CCC(H)Ph}(PPh 3 )]-[BF 4 ] (4) after stirring for 15 min at room temperature. Complex 4 evolves to [Ir(η 5 -C 5 Me 5 ){κ 4 (P,C,C,C)-PPh 2 C 6 H 4 C(Ph)CHCC(H)-Ph}][BF 4 ] ( 5) after stirring for 24 h at room temperature. The reaction of complex 2a with methyl trifluoromethanesulfonate leads to the formation of the complex [Ir(η 5 -C 5 Me 5 ){κ 3 (C,C,C)-C 6 H 4 C(Me)CCC(H)Ph}(PPh 3 )][CF 3 SO 3 ] as a 1:1.5 mixture of the Z (6) and E (7) stereoisomers. The structures of complexes 2c, 5, and 7 have been resolved by X-ray diffraction analysis.