Reactions of [Cp*Ir(η 3 -CH 2 CHCHPh)(NCMe)]OTf (1) with protic amines, alcohols, and water produce amidine complexes [Cp*Ir(η 3 -CH 2 CHCHPh)(NHdC Et (b), i-Pr (c)), and amido complex Cp*Ir(η 3 -CH 2 CHCHPh)(NHC(dO)Me) (5-K), respectively. The keto form amido complex 5-K undergoes tautomerization to give the enol form complex Cp*Ir(η 3 -CH 2 CHCHPh)(Nd C(OH)Me) (5-E) in polar solvents. Tertiary amines (NMe 3 , NEt 3 ) react with 1 in chlorinated solvents (XCl) to give the chloro complex Cp*IrCl(η 3 -CH 2 CHCHPh) (3) and quaternary ammonium salts [R 3 NX]OTf (R ) Me, Et and X ) CH 2 Cl, CH 3 , CHCl 2 , CCl 3 , PhCH 2 ). Crystal structures of 2a, 4a, 5-K, and [Cp*Ir(NHdC(OH)Me)(OH 2 )(PPh 3 )]OTf 2 (6) have been determined by single-crystal X-ray diffraction analysis, which lead us to suggest hybrid structures, Ir--NH-C(dN + Me 2 )Me (2a′) for 2a and Ir--NH-C(dO + Me)Me (4a′) for 4a to some extent. Complexes 2 and 4 react with PPh 3 to give an iridium(III) complex [Cp*Ir(η 3 -CH 2 CHCHPh)(PPh 3 )]OTf (7) and the free amidines NHdC(NR 2 )Me ( 8) and imino-ethers NHdC(OR′)Me (9), respectively. Nitrile complexes 1 and [Cp*Ir(η 3 -CH 2 CHCHPh)(NCCHd CHMe)]OTf (10) catalyze the hydration of the nitriles in the presence of Na 2 CO 3 to produce amides, and the benzonitrile complex [Cp*Ir(η 3 -CH 2 CHCHPh)(NCPh)]OTf (11) catalyzes the methanolysis of benzonitrile in the presence of Na 2 CO 3 to produce NHdC(OMe)Ph. Plausible mechanisms for these catalytic reactions are suggested with the amido and imino-ether complexes such as 4 and 5 being involved.

Reaction of the (alkyl)(alkenyl)(alkynyl)iridium(III) complex [Ir(CH3)(CHCHNEt3)(C⋮C(p-C6H4CH3))(CO)(PPh3)2]ClO4 (3) with aqueous HCl initiates an intramolecular coupling reaction between −CH3 and −C⋮C(p-C6H4CH3) groups to give [Ir(C(CH3)CH(p-C6H4CH3)(CHCHNEt3)(Cl)(CO)(PPh3)2]ClO4 (5), which further reacts with aqueous HCl to produce [Ir(CHCHNEt3)(Cl)2(CO)(PPh3)2]ClO4 (6) and cis-CH3CHCH(p-C6H4CH3) (7). Complex 5 yields the C−C coupling product [(p-C6H4CH3)HCC(CH3)CHCHNEt3]ClO4 (8) when it is refluxed in CHCl3. The (alkyl)bis(alkynyl)iridium(III) compound Ir(CH3)(C⋮C(p-C6H4CH3))2(CO)(PPh3)2 (4) reacts with aqueous HCl to give H2CCCH(p-C6H4CH3) (9). Complex 3 reacts with excess DCl to give the d 5 isotopomer CD3CDCD(p-C6H4CH3) (7- d 5 ), while the reaction of 4 with DCl gives the d 1 isotopomer H2CCCD(p-C6H4CH3) (9- d 1 ). Plausible reaction pathways are discussed for the formation of 7 and 9 and for the H/D exchange to give the isotopomer 7- d 5 .

Stable alkynyl complexes of iridium(III) (L(n)Ir-triple bond-R) that are prepared from the reactions of terminal alkynes readily undergo the intramolecular C-C bond-forming reactions between the alkynyl and adjacent hydrocarbyl ligands to yield conjugated olefins. These reactions are initiated by electrophiles (H(+), Me(+)) that attack the beta carbon of the alkynyl ligand to increase the electrophilicity of the alpha carbon of the alkynyl ligand. The C-C bond is then formed between the alpha carbons of the alkynyl and adjacent hydrocarbyl ligands.

cis-Bis(alkenyl)iridium complexes cis,trans-[IrR(-CHdCH, CH 3 (b), Cl (c)) have been prepared from the reactions of dihaloiridium(III) compounds with HCtCH and PPh 3 . Reactions of 2b and 2c with CH 2 dCHCH 2 Br give bis(alkenyl)-(PPh 3 )iridium, cis-[IrBr(CH 3 )(-CHdCH + PPh 3 ) 2 (CO)(PPh 3 )] + , and cis,cis-[IrBr 2 (-CHdCH-+PPh 3 ) 2 (CO)(PPh 3 )] + . Crystal structures of 2c and [Ir(OClO 3 )(CH 3 )(H 2 O)(CO)(PPh 3 ) 2 ] + (4) have been determined by X-ray diffraction data analysis.Attempts to mount crystals of 2a and 2b on a X-ray diffractometer have failed due to the collapse of the