Synthesis and characterization of half-sandwich Rh, Ir complexes containing mono-thiolate-ortho-carborane ligand

Two binuclear complexes [Cp^∗M(Cl)Carb^S]₂ (Cp^∗ = η⁵-C₅Me₅, M = Rh (1a), Carb^S = SC₂(H)B₁₀H₁₀, Ir (1b)) were synthesized by the reaction of LiCarb^S with the dimeric metal complexes [Cp^∗MCl(μ-Cl)]₂ (M = Rh, Ir). Four mononuclear complexes Cp^∗M(Cl)(L)Carb^S (L = BuⁿPPh₂, M = Rh (2a), Ir (2b); L = PPh₃, M = Rh (4a), Ir (4b)) were synthesized by reactions of 1a or 1b with L (L = BuⁿPPh₂ (2); PPh₃ (4)) in moderate yields, respectively. Complexes 3a, 3b, 5a, 5b were obtained by treatment of 2a, 2b, 4a, 4b with AgPF₆ in high yields, respectively. All of these compounds were fully characterized by IR, NMR, and elemental analysis, and the crystal structures of 1a, 1b, 2a, 2b, 4a, 4b were also confirmed by X-ray crystallography. Their structures showed 3a, 3b and 5a, 5b could be expected as good candidates for heterolytic dihydrogen activation. Preliminary experiments on the dihydrogen activation driven by these half-sandwich Rh, Ir complexes were done under mild conditions.     

Straightforward synthesis of phosphametallocenium cations of Rh and Ir

Reaction of 3,4-dimethylphospholylthallium (Tl-1) with [Cp^∗MCl₂]₂ (M = Rh, Ir) leads to the formation of the dimeric species [(Cp^∗M)₂(Me₂C₄H₂P)₃]⁺2 and 3 with bridging μ-η¹:η¹-phospholyl ligands. The phosphametallocenium sandwich complexes [Cp^∗M(Me₂C₄(SiMe₃)₂P)]⁺7 (M = Rh) and 8 (M = Ir) could be obtained from the reaction of [Cp^∗MCl₂]₂ and the 2,5-bis(trimethylsilyl)-1-trimethylstannylphosphole 6, with the bulky trimethylsilyl groups preventing the phosphole from η¹- and enforcing a η⁵-coordination. The structures of phospharhodocenium cation 7 and a byproduct 9 containing a phosphairidocenium moiety could be determined by X-ray diffraction.     

Synthesis of sulfido- and thiolato-bridged Ir3 cluster and its reactions with alkyne and isocyanide including highly regioselective cyclotrimerization of methyl propiolate

Reactions of a sulfido- and thiolato-bridged diiridium complex [(Cp^∗Ir)₂(μ-S)(μ-SCH₂CH₂CN)₂] (Cp^∗ = η⁵-C₅Me₅) with [(Cp^∗MCl)₂(μ-Cl)₂] (M = Ir, Rh) afforded the sulfido- and thiolato-bridged trinuclear clusters [(Cp^∗M)(Cp^∗Ir)₂(μ₃-S)(μ₂-SCH₂CH₂CN)₂(μ₂-Cl)]Cl (4: M = Ir, 5: M = Rh). Upon treatment with XyNC (Xy = 2,6-Me₂C₆H₃) in the presence of KPF₆ at 60 °C, 4 was converted into a mixture of a mononuclear XyNC complex [Cp^∗Ir(SCH₂CH₂CN)(CNXy)₂][PF₆] (6) and a dinuclear XyNC complex [{Cp^∗Ir(CNXy)}₂(μ-S)(μ-SCH₂CH₂CN)][PF₆] (7). On the other hand, reactions of 4 and 5 with methyl propiolate in the presence of KPF₆ at 60 °C resulted in the formation of a cyclic trimer of the alkyne 1,3,5-C₆H₃(COOMe)₃ as the sole detectable organic product. The reactions proceeded catalytically with retention of the cluster cores of 4 and 5, whereby the activity of the former was much higher than that of the latter.     

Synthesis and characterization of half-sandwich iridium complexes containing 2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene and ancillary ortho-carborane-1,2-dichalcogenolato ligands

The binuclear half-sandwich iridium complexes {Cp^∗IrCl₂}₂(μ-2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene) (3) and {Cp^∗Ir[E₂C₂(B₁₀H₁₀)]}₂(μ-2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene) (E = S(5a), Se(5b)) were prepared from the reaction of [Cp^∗IrCl(μ-Cl)]₂ or the “pseudo-aromatic” half-sandwich iridium complex Cp^∗Ir[E₂C₂(B₁₀H₁₀)] (E = S(4a), Se(4b)) with a tetrathiafulvalene (TTF) derivative 2,6-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene (2) at room temperature. The complexes (3, 5a and 5b) have been fully characterized by IR and NMR spectroscopy, as well as elemental analysis. And the molecular structures of 2 and 5a were established through X-ray crystallography. It is interesting that infinite tunnels are created by repeating ‘buckled bowl’ molecules of 5a.     

Reactions of 2-pyridinethiolate cobalt(III) complexes with pyridinethiolate or benzenethiolate ligands

Four half-sandwich cobalt complexes, Cp^∗Co(2-PyS)₂ (2), Cp^∗Co(2-PyS)₂ · HI (3), Cp^∗Co(2-PyS) (4-PyS) (4), (Cp^∗Co)₂(μ-PhS)₂(μ-2-PyS)I (5) [Cp^∗ = pentamethylcyclopentadienyl, 2-PyS = 2-pyridinethiolate, 4-PyS = 4-pyridinethiolate, PhS = benzenethiolate] were successfully synthesized by the reactions of 2-pyridinethione, lithium 4-pyridinethiolate and lithium benzenethiolate with Cp^∗Co(2-PyS)I (1), respectively. Complexes 2 and 3 have the structures with two 2-pyridinethiolates ligands coordinated to the cobalt atom. Two different pyridinethiolates ligands can be identified in complex 4. The molecular structure of 5 consists of two Cp^∗-Co fragments, which are triply bridged by three sulfur atoms from different ligands. The molecular structures of 3 and 5 were determined by X-ray crystallographic analysis. All the complexes have been well characterized by elemental analysis, NMR and IR spectra.     

Catalytic hydrogenation of CO and CN bonds via heterolysis of H2 mediated by metal-sulfur bonds of rhodium and iridium thiolate complexes

Coordinatively unsaturated rhodium and iridium complexes having a bulky thiolate, [Cp∗M(PMe₃)(SDmp)](BAr^F₄) (1a: M = Rh; 1b: M = Ir; Dmp = 2,6-(mesityl)₂C₆H₃, Ar^F = 3,5-(CF₃)₂C₆H₃), catalyzed the hydrogenation of benzaldehyde, N-benzylideneaniline, and cyclohexanone, under 1 atm of H₂ at low temperatures. In these catalytic reactions, the M-H/S-H complexes [Cp∗M(PMe₃)(H)(HSDmp)](BAr^F₄) (2a: M = Rh; 2b: M = Ir) generated via H₂ heterolysis by 1a or 1b were suggested to transfer both M-H hydride and S-H proton to substrates. The catalytic reactions were terminated by the dissociation of H-SDmp from the metal centers of 2a and 2b that occurs at ambient temperature under H₂ atmosphere.     

Synthesis and characterization of hetero-binuclear Co-Rh complexes [CpCoS2C2(B9H10)][Rh(COD)] and [CpCoSe2C2(B10H10)][Rh(COD)]

Two hetero-binuclear complexes [Cp^∗CoS₂C₂(B₉H₁₀)][Rh(COD)] (2a) and [Cp^∗CoSe₂C₂(B₁₀H₁₀)][Rh(COD)] (2b) [Cp^∗ = η⁵-pentamethylcyclopentadienyl, COD = cyclo-octa-1,5-diene (C₈H₁₂)] were synthesized by the reactions of half-sandwich complexes [Cp^∗CoE₂C₂(B₁₀H₁₀)] [E = S (1a), Se (1b)] with low valent transition metal complexes [Rh(COD)(OEt)]₂ and [Rh(COD)(OMe)]₂. Although the reaction conditions are the same, the structures of two products for dithiolato carborane and diselenolato carborane are different. The cage of the carborane in 2a was opened; However, the carborane cage in 2b was intact. Complexes 2a and 2b have been fully characterized by ¹H, ¹¹B NMR and IR spectroscopy, as well as by elemental analyses. The molecular structures of 2a and 2b have been determined by single-crystal X-ray diffraction analyses and strong metal-metal interactions between cobalt and rhodium atoms (2.6260 Å (2a) and 2.7057 Å (2b)) are existent.     

Heterobimetallic complexes as oxygen donor bidentate ligands: synthesis of early-late trinuclear complexes

The early-late heterometallic complexes [TiCp^∗((OCH₂)₂Py)(μ-O)M(COD)] (M = Rh, Ir) behave as four-electron donor ligands yielding the polynuclear cationic complexes [TiCp^∗(OCH₂)₂ Py(μ-O){M(COD)}₂]OTf (M = Rh (1), Ir (2)). The molecular structure of complex 1 has been established through an X-ray diffraction study.     

Synthesis and characterization of heterometallic Rh/Ru complexes supported by 1,2-dichalcogenolato-o-carborane ligands

The 16-electron half-sandwich complexes Cp^∗Rh[E₂C₂(B₁₀H₁₀)] (E = S, 1a; Se, 1b) react with [Ru(COD)Cl₂]_x under different conditions to give different types of heterometallic complexes. When the reactions were carried out in THF for 24 h, the binuclear Rh/Ru complexes [Cp^∗Rh(μ-Cl)₂(COD)Ru][E₂C₂(B₁₀H₁₀)] (E = S, 2a; Se, 2b) bridged by two Cl atoms and the binuclear Rh/Rh complexes (Cp^∗Rh)₂[E₂C₂(B₁₀H₁₀)] (E = S, 3a; Se, 3b) with direct Rh-Rh bond can be isolated in moderate yields. [Ru(COD)Cl₂] fragments in 2a and 2b have inserted into the Rh-E bond. If the [Ru(COD)Cl₂]_x was reacted with 1a in the presence of K₂CO₃ in methanol solution, the product [Cp^∗Rh(COD)]Ru[S₂C₂(B₁₀H₁₀]] (4a), K[(μ-Cl)(μ-OCH₃)Ru(COD)]₄ (5a) and 3a were obtained. The B(3)-H activation in complex 4a was found. However, when the reaction between 1b and [Ru(COD)Cl₂]_x was carried out in excessive NaHCO₃, the carborane cage opened products {Cp^∗Rh[S₂C₂(B₉H₁₀)]}Ru(COD) (6b), {Cp^∗Rh[S₂C₂(B₉H₉)]}Ru(COD)(OCH₃) (7b) and 3b were obtained. All complexes were fully characterized by their IR, ¹H NMR and elemental analyses. The molecular structures of 2a, 2b, 3b, 4a, 5a, and 7b have been determined by X-ray crystallography.     

Formation of niobium and tantalum ylide complexes

The reactions of tri(bis(ethyl)amino)phosphorus ylide (Et₂N)₃PCH₂ with cyclopentadienyl (Cp) metal (V) tetrachloride CpMCl₄ (M = Nb 1; Ta 3) and pentamethylcycopentadienyl (Cp^∗) metal (V) tetrachloride Cp^∗MCl₄ (M = Nb 2; Ta 4) were investigated. The hexa-coordinate ylide adducts complexes 5 (CpNbCl₄(H₂CP(NEt₂)₃)), 6 (Cp^∗NbCl₄(H₂CP(NEt₂)₃)) and 8 (Cp^∗TaCl₄(H₂CP(NEt₂)₃)) with pseudo-octahedral geometry were structurally analyzed with X-ray diffraction. Compound 4 (Cp^∗TaCl₄) reacted with three molar equivalent of phosphorus ylide to form one ionic complex 9 ([H₃C-P(NEt₂)₃][Cp^∗TaCl₅]) which was also structurally analyzed with X-ray diffraction. The possible formation mechanism of compound 9 has been discussed.     

Spectroscopic and structural characterization of cationic N-(2-aminoethyl)aziridine-N,N′ chelate complexes of the d-metals Rh(III) and Ir(III)

The syntheses of the compounds [M(Cp^∗)(aeaz)(az)](OTf)₂ (4, 5) (M = Rh(III), Ir(III); aeaz = C₂H₄NC₂H₄NH₂, az = C₂H₄NH (3)) containing cationic N-(2-aminoethyl)aziridine-N,N′ chelate complexes are described. The bis-aziridine complexes [MCl(Cp^∗)(az)₂]Cl (M = Rh (1), M = Ir (2)) react with an excess of the aziridine (az) in the presence of AgO₃SCF₃ (=AgOTf) via AgCl precipitation and az addition followed by a metal-mediated coupling reaction, to give the compounds [M(Cp^∗)(aeaz)(az)](OTf)₂ (4, 5). The new aeaz ligand is formally the dimerisation product of az. Using the same reaction conditions with the analogous, but weaker Lewis acidic ruthenium(II) complex [RuCl(C₆Me₆)(az)₂]Cl (6) an anion exchange reaction yielding [RuCl(C₆Me₆)(az)₂]OTf (8) is observed. After purification, all compounds are fully characterized using IR, FAB-MS, ¹H and ¹³C NMR spectroscopy. The single crystal X-ray structure analysis reveals a distorted octahedral geometry for all complexes.     

Synthesis and structural aspects of M-allyl (M = Ir, Rh) complexes

The synthesis, characterization and chemistry of novel η³-allyl metal complexes (M = Ir, Rh) are described. The structures of compounds (C₅Me₄H)Ir(PPh₃)Cl₂ (1), (C₅Me₄H)Ir(PPh₃)(η³-1-methylallyl)Br (3a), (C₅Me₄H)Ir(η⁴-1,3,5-hexatriene) (8), and (C₅Me₅)Rh(η³-1-ethylallyl)Br (5d) have been determined by X-ray crystallography. Structural comparisons among these complexes are discussed. It is found that the neutral metal allylic complex [Cp^∗IrCl(η³-methylallyl)] (5) ionizes in polar solvents to give [Cp^∗Ir(η³-methylallyl)]⁺Cl⁻ (6) and reaches equilibrium (5 ? 6) at room temperature. Addition of tertiary phosphine ligands to neutral complexes such as [Cp^∗Ir(η³-methylallyl)Cl], results in the formation of stable ionic phosphine adducts. Factors such as solvent, length of carbon chain, temperature and light are discussed with respect to the formation, stability and structure of the allyl complexes.     

Organometallic dithiolene complexes of benzenedithiolate analogues with π-coordinating and π-interacting Cp* ligand

Organometallic dithiolene complexes, which were formulated as [Cp*M(dcbdt)] and [Cp*M(dcdmp)] (M = Co, Rh, Ir; Cp* = η⁵-pentamethylcyclopentadienyl, dcbdt = 4,5-dicyanobenzene-1,2-dithiolate, dcdmp = 2,3-dicyano-5,6-dimercaptopyrazine) were prepared from a low valent Cp*Co^I or high valent Cp*M^III species (M^III = Co^III, Rh^III, Ir^III). The UV-Vis absorption spectral and electrochemical data of them were obtained. The lowest absorption (HOMO-LUMO) energies of them became redshift in order of the Co > Rh > Ir complexes. The reduction potentials suggested that the central metal modifies their LUMO levels. The molecular and crystal structures of [Cp*Co(dcbdt)] (3a), [Cp*Co(dcdmp)] (4a) and [Cp*Rh(dcdmp)] (4b) were determined by X-ray diffraction studies. The cobalt complexes 3a and 4a were monomeric, formally 16-electron complexes and have two-legged piano-stool geometries. The crystal structure of 3a indicated some plane-to-plane intermolecular interactions such as benzene?benzene interaction on the dcbdt ligand and two Cp*?benzene π-π stackings. 4a showed plane-to-plane interaction with a pseudo-4-fold-symmetry arrangement between the pyrazine moieties on the dcdmp ligand. The rhodium complex 4b was dimeric in the crystal to form a criss-cross arrangement and had a three-legged piano-stool geometry, but it was monomerized in solution. The dimer of 3b was observed in the oxidation process of the cyclic voltammogram.     

Binuclear iridium complexes containing bridging 1,2-dicarba-closo-dodecaborane-1,2-dichalocogenolato ligands: Molecular structures of the complexes [(CODIr)2(μ2-S2C2(B10H10))] and [(CpIr)2(μ2-Se2C2(B10H10))]

Four binuclear iridium complexes with a chelating 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolate ligands [Ir₂(COD)₂(μ₂-E₂C₂B₁₀H₁₀)] [E = S (3a), Se (3b)] [(Cp^∗Ir)₂(μ₂- E₂C₂B₁₀H₁₀)] [E = S (5a), Se (5b)] have been synthesized through different method. The formal oxidation state of iridium in complexes 3 and 5 are I and II, respectively, due to the different electron donor coordinated to the iridium center. All four complexes 3a-5b are characterized by IR, ¹H, ¹³C, ¹¹B NMR spectra and elemental analyses. The molecular structures of complex 3a and 5b have been determined by X-ray crystallographic analysis, only 5b shows the metal-metal interaction between the two iridium atoms.     

Self-assembly directed by C-H activation: Synthesis and characterization of [(CpIr)2(R-NC-Ph-CNR)]2(4,4-bipyridine)2·(OTf)4 (R = Ph, Me)

Self-assembly of a novel class of bis-imine-cyclometalated macrocycles [(Cp^∗Ir)₂(Ph-NC-Ph-CN-Ph)]₂(4,4′-bipyridine)₂·(OTf)₄ (3a) and [(Cp^∗Ir)₂(Me-NC-Ph-CN-Me)]₂(4,4′-bipyridine)₂·(OTf)₄ (3b) was directed by double-site C-H activations of aromatic bis-imine substrates. Two synthetic routes were established, using either (i) binuclear cyclometalated complexes (Cp^∗Ir)₂L1Cl₂ (1a) and (Cp^∗Ir)₂L2Cl₂ (1b) or (ii)4,4′-bipyridine(bpy)-bridged complex (Cp^∗IrCl₂)₂(bpy) (2) as starting materials. All the products were characterized by IR, ¹H NMR and EA. Isomers were found in macrocyclic complexes, which were thermodynamically stable from reversible transformation in days. Highly robust structure of the cyclometalated macrocycles was indicated by the existence of stable isomer pairs. One isomer of 3b was determined by single-crystal X-ray diffraction. It was a rare case for half-sandwich metallosupramolecular macrocycles that weak interactions between macrocycles and OTf ions were fully captured in detail, and were demonstrated to be essential for the maintenance of tunnel structures of macrocycles in crystal packing.     

Synthesis, structure and characterization of dimolybdaheteroboranes

Chalcogen-stabilized dimolybdaboranes 3-5 (3: [(Cp^∗Mo)₂B₄H₅Se(Ph)], 4: [(Cp^∗Mo)₂B₄H₃Se₂(SeCH₂Ph)] and 5: [(Cp^∗Mo)₂B₃H₆(BSR)(μ-η¹-SR)] (R = 2,6-(^tBu)₂-C₆H₂OH)) have been isolated from the mild pyrolysis of dichalcogenide ligands, RE-E‘R (R = Ph: E = S, E‘ = Se; R = CH₂Ph, [2,6-(^tBu)₂-C₆H₂OH]: E = E‘ = Se, S) and [(Cp^∗Mo)₂B₄H₈], 2, an intermediate generated from the reaction of [Cp^∗MoCl₄] (1) (Cp^∗ = η⁵-C₅Me₅), with [LiBH₄.thf]. The geometry of [(Cp^∗Mo)₂B₄H₅Se(Ph)] is similar to that of [(Cp^∗Mo)₂B₅H₉], in which one BH₃ unit on the open face is replaced by a triple bridged selenium atom. All the compounds have been characterized in solution by ¹H, ¹¹B, ¹³C NMR and IR spectroscopy and elemental analysis. The structural types were unequivocally established by X-ray crystallographic analysis of compounds 3-5.     

Half-sandwich rhodium complexes containing both N-heterocyclic carbene and ortho-carborane-1,2-dithiolate ligands

A new route was used to synthesize half-sandwich rhodium complexes containing both N-heterocyclic carbenes (NHC) and carborane ligands. The rhodium carbene complexes Cp^∗Rh(L)[S₂C₂(B₁₀H₁₀)] (Cp^∗ = pentamethylcyclopentadienyl, L = 1,3-dimethylimidazolin-2-ylidene; 4) can be obtained from the reaction of Cp^∗Rh(L)Cl₂ (2) with Li₂S₂C₂(B₁₀H₁₀) or from the reaction of Cp^∗Rh[S₂C₂(B₁₀H₁₀)] (3) with silver-NHC complex prepared by direct reaction of an imidazolium precursor and Ag₂O. Complexes 2 and 4 were characterized by IR, NMR spectroscopy, element analysis and X-ray structure analyses.     

A combined experimental and theoretical study of metallic salts of thiapentadienyl, sulfinylpentadienyl and butadienesulfonyls

Alternative methods for the synthesis of the following acyclic salts (CH₂CHCHCHS)M [M = K, 1(K); Na, 1(Na); Li, 1(Li)], (CH₂CHCHCHSO)M [M = K, 2(K); Na, 2(Na)], (CH₂CHCHCHSO₂)M [M = K, 3(K); Na, 3(Na); Li, 3(Li)], (CH(Me)CHC(Me)CHSO₂)M [Me5-syn, M = K, 9(K); Na, 9(Na); Li, 9(Li), (CH(Me)CHCHC(Me)S)M [Me5-syn, M = K, 10(K); Na, 10(Na); Me5-anti, M = K, 11(K); Na, 11(Na)] are described, as a result of the activation of C-S bond in dihydrothiophenes by deprotonation with different bases. The effect of methyl substituents in the dihydrothiophenes is significant, which modifies considerably the choice of the base. The influence of the reaction conditions, type of solvent, base and dihydrothiophenes is analyzed. The NMR spectroscopy, including NOESY, ROESY and difference NOE establish the preferred U conformation for all derivatives, and support a delocalization of charge on the thiapentadienyl (1M) and sulfinylpentadienyl (2M) complexes. However, a conjugated diene structure is proposed on the butadienesulfonyl compounds (3M), in which the negative charge is delocalized in the SO₂ fragment and stabilized with the corresponding cations (M = K, Na and Li). In presence of traces of base, compounds 3M suffer a rearrangement, to the most stable S conformer, 13M. The stability of 3M depends on the size of the cation, the greater the size, the greater stability. Furthermore, a theoretical study shows that electronic and geometrical properties (energy conformers, charge distributions and relative stabilities) of the thiapentadienyl, sulfinylpentadienyl and butadienesulfonyl anions and their corresponding metal salts 1M-3M (M = Li, Na and K) shows to be in good agreement with the experimental findings.     

Half-sandwich Ru(II), Ir(III) and Rh(III) complexes with bridging or chelating N-heterocyclic bis-carbene ligand: Synthesis and characterization

N-heterocyclic bis-carbene ligand (bis-NHC) which was derived from 1,1′-diisopropyl-3,3′-ethylenediimidazolium dibromide (L·2HBr) via silver carbene transfer method, reacted with [(η⁶-p-cymene)RuCl₂]₂ and [Cp^∗MCl₂]₂ (Cp^∗ = η⁵-C₅Me_5, M = Ir, Rh) respectively, afforded complexes [(η⁶-p-cymene)RuCl₂]₂(L) (1), [Cp^∗IrCl₂]₂(L) (2) and [Cp^∗RhCl(L)][Cp^∗RhCl₃] (3). When [Cp^∗IrCl₂]₂ was treated with 2 equiv AgOTf at first, and then reacted with bis-NHC ligand, [Cp^∗IrCl(L)]OTf (4) was obtained. The molecular structures of complexes 1-4 were determined by X-ray single crystal analysis, showing that 1 and 2 adopted bridging coordination mode, 3 and 4 adopted chelating coordination mode. All of these complexes were characterized by ¹H, ¹³C NMR spectroscopy and element analysis.     

Insertion of nitrene and chalcogenolate groups into the Ir-C σ bond in a cyclometalated iridium(III) complex

Treatment of [Cp∗Ir(ppy)Cl] (Cp∗ = η⁵-C₅Me₅, ppyH = 2-(2-pyridyl)phenyl) with Ag(OTf) (OTf⁻ = triflate) in MeOH and MeCN gave the solvento complexes [Cp∗Ir(ppy)(solv)][OTf] (solv = MeOH (1) and MeCN (2)). Complex 1 is capable of catalyzing oxidation and azirdination of styrene with PhIO and PhINTs (Ts = tosyl), respectively. Treatment of 2 with a stoichiometric amount of PhINTs resulted in the insertion of the NTs group into the Ir-C(ppy) bond and formation of [Cp∗Ir(η²-ppy-NTs)(MeCN)][OTf] (3). Treatment of 1 with R₂E₂ afforded [Cp∗Ir(ppy)(η¹-R₂E₂)][OTf] (E = S (4), Se (5), Te (6)). Reactions of 4 and 5 with Ag(OTf) resulted in cleavage of the E-E bond and insertion of an ER group into the Ir-C(ppy) bond. The crystal structures of complexes 2-6 and [Cp∗Ir(η²-ppy-S-p-tol)(H₂O)][OTf]₂ have been determined.