Chemistry of Iridium(I) Cyclooctadiene Compounds with Thiapentadienyl, Sulfinylpentadienyl, and Butadienesulfonyl Ligands

Gamero‐Melo, Prócoro; Melo-Trejo, Patricia Andrea; Cervantes-Vásquez, Marisol; Mendizabal-Navarro, Nelly Paola; Paz‐Michel, Brenda; Villar-Masetto, Tere Isabel; González‐Fuentes, Miguel A.; Paz-Sandoval, M. Ángeles

doi:10.1021/om2007166

Cited by 16 publications

(6 citation statements)

References 67 publications

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“…The Ir–S bond distances are close to those reported for Ir(III)–S complexes . The S–O distances (1.477(6), 1.467(6), 1.471(6), and 1.485(6) Å) and OSO angles (111.7(4) o and 112.1(4) o ) are in the range observed for other sulfinates (1.431–1.490 Å; 111.7°–116.1°). ,,,, …”

Section: Results and Discussionsupporting

confidence: 78%

Synthesis and Spectroscopy of Anionic Cyclometalated Iridium(III)-Dithiolate and -Sulfinates—Effect of Sulfur Dioxygenation on Electronic Structure and Luminescence

Nguyễn

Chew

et al. 2014

Inorg. Chem.

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A new anionic heteroleptic Ir(III)-dithiolate complex Ir(ppy)2(benzene-1,2-dithiolate) (ppy = 2-phenylpyridine, [IrSS](-)) undergoes very fast air oxidation to form a monosulfinate complex [IrSSO2](-), which can be further dioxygenated by O2 or H2O2 to give a disulfinate complex [IrSO2SO2](-), which has been characterized by X-ray crystallography. The dioxygenation is accompanied by changes in the electronic structures of the complexes, leading to blue shift of emission from [IrSS](-) (λ(max) = 665 nm) to [IrSSO2](-) (λ(max) = 556 nm) and to [IrSO2SO2](-) (λ(max) = 460 nm). The molecular and electronic structures of the complexes are probed by DFT calculations. Time-dependent DFT (TD-DFT) calculations show the lowest energy spin-allowed electronic transitions for [IrSS](-) and [IrSSO2](-) are mainly ligand (3p orbital of S)-to-ligand (π* orbitals of ppy)-charge-transfer transition, whereas the lowest energy electronic transition in [IrSO2SO2](-) is predominantly metal-to-ligand-charge transfer in nature.

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Section: Results and Discussionsupporting

confidence: 78%

Synthesis and Spectroscopy of Anionic Cyclometalated Iridium(III)-Dithiolate and -Sulfinates—Effect of Sulfur Dioxygenation on Electronic Structure and Luminescence

Nguyễn

Chew

et al. 2014

Inorg. Chem.

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“…The bridging CO in 2 was slightly nonsymmetric to the iridium atoms with bond lengths of 2.075(4) and 2.106(4) Å for Ir1–C23 and Ir2–C23, respectively. The Ir–P bond in 3 [2.398(3) Å] was quite similar to related compounds, such as (η 4 -COD)Ir(η 1:2 -CH 2 CHCHCHSO 2 )PMe 3 [2.398(2) Å] and 7 [2.3865(12) Å], and longer than those of 5 [2.3492(12) Å], 6 [2.3506(9) Å], and 8 [2.3578(9) Å], vide infra.…”

Section: Resultsmentioning

confidence: 80%

“…The chloro ligand can be removed in the presence of AgX (X = BF 4 , PF 6 ) to afford the corresponding cationic complexes [Cp*M(η 5 -CH 2 C(Me)CHC(Me)O][X] (M = Rh, X = BF 4 ; M = Ir, X = PF 6 ), while an organometallic polymer with a μ 3 -bridging iridaoxabenzene ligand is isolated if a bulkier 2,4- t -Bu-oxopentadienyl ligand is used . As an extension of the chemistry of the heteropentadienyl ligands, we decided to explore their reactivity with [(η 4 -COD)Ir(μ 2 -Cl)] 2 (COD = cyclooctadiene), thus finding dimeric structures, which include μ 2 -bridging thia- and sulfinylpentadienyl ligands, as well as compound (η 4 -COD)Ir(μ 2 -Cl)(η 1 -μ 2 -η 1:2 -OSOCHCHCHCH 2 )Ir(η 4 -COD), which showed the dioxo-thiapentadienyl ligand bonding in an intermolecular fashion, as a sulfinato-O,S complex . Previously, the reaction of [(η 6 -C 6 Me 6 )RuCl 2 ] 2 with the trimethylsililoxybutadiene CH 2 CHCHCHOSiMe 3 provides an unexpected contrast, in which a dinuclear oxopentadienyl product, [(η 6 -C 6 Me 6 )Ru(η 1:3 -μ 2 - exosyn -CH 2 CHCHCHO)] 2 (BF 4 ) 2 , has been isolated and structurally characterized.…”

Section: Introductionmentioning

confidence: 99%

Iridaoxacyclohexadiene-Bridged Mixed-Valence Iridium Cyclooctadiene Complex: Oxidative Addition and Hydrogen-Transfer to Coordinated Cyclooctadiene

et al. 2014

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The systematic exploration of the synthesis of heteropentadienyl metal complexes leads us to study the metathesis reaction of [(η 4 -COD)Ir(μ 2 -Cl)] 2 with lithium 2,4-dimethyloxopentadienide, which affords the dinuclear Ir 0 −Ir II compound (η 4 -COD)Ir[η 1:1 -μ 2 -η 4 -CHC(Me)CHC(Me)O)]-Ir(η 4 -COD) (1) with a metal−metal bond. The COD ligands are coordinated η 4 to each Ir center, whereas the oxopentadienyl ligand is bridging both Ir atoms, allowing the formation of a novel iridapyran complex with Ir II and bonding η 4 with Ir 0

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“…Attempts to prepare open cobaltocenes [Co(η 5 -Pdl) 2 ] have been unsuccessful, and instead reduction to Co(I) has been observed . However, cationic pentadienyl Co(III) complexes can be stabilized by a (η 5 -C 5 H 5 )Co or (η 5 -C 5 Me 5 )Co fragment. , For the heavier cobalt congener iridium, iridium(I) heteropentadienyl complexes such as [(η 4 -COD)Ir(μ 2 -1-2,5-η-CH 2 CHCHCHSO)] 2 and cationic iridium(III) pentadienyl complexes such as [(η 5 -C 5 H 5 )Ir(η 5 -C 5 H 5 Me 2 -2,4)][BF 4 ] have only recently been reported.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Coordination Chemistry of an Enantiomerically Pure Pentadienyl Ligand

et al. 2013

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The coordination chemistry of the enantiomerically pure dimethylnopadienyl ligand (Pdl*) with early to late transition metals is presented. Dimethylnopadiene is prepared by a Wittig reaction from (1R)-(−)-myrtenal, which is readily available from the chiral pool. Deprotonation of dimethylnopadiene with a Schlosser base gives K(Pdl*), which is a good starting material for the preparation of the early- to late-transition-metal open metallocenes [M(η5-Pdl*)2] (M = Ti, V, Cr, Fe) and mono(pentadienyl) complexes [(η5-Cp′)Fe(η5-Pdl*)] (Cp′ = 1,2,4-(Me3C)3C5H2), [(η7-C7H7)Zr(η5-Pdl*)], and [(η4-COD)Ir(η5-Pdl*)]. These complexes have been fully characterized by several spectroscopic techniques, elemental analysis, and X-ray crystallography. In all of these cases the Pdl* ligand exhibits excellent face selectivity upon metal coordination, because it coordinates exclusively from the sterically less hindered site of the bicyclic ligand framework. Within the series of open metallocenes [M(η5-Pdl*)2] (M = Ti, V, Cr, Fe) the open ferrocene is the least thermally stable molecule and degrades to iron metal in solution. This instability is attributed to the severe steric demand of this ligand system in combination with the relatively small Fe2+ center.

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Chemistry of Iridium(I) Cyclooctadiene Compounds with Thiapentadienyl, Sulfinylpentadienyl, and Butadienesulfonyl Ligands

Cited by 16 publications

References 67 publications

Synthesis and Spectroscopy of Anionic Cyclometalated Iridium(III)-Dithiolate and -Sulfinates—Effect of Sulfur Dioxygenation on Electronic Structure and Luminescence

Synthesis and Spectroscopy of Anionic Cyclometalated Iridium(III)-Dithiolate and -Sulfinates—Effect of Sulfur Dioxygenation on Electronic Structure and Luminescence

Iridaoxacyclohexadiene-Bridged Mixed-Valence Iridium Cyclooctadiene Complex: Oxidative Addition and Hydrogen-Transfer to Coordinated Cyclooctadiene

Synthesis and Coordination Chemistry of an Enantiomerically Pure Pentadienyl Ligand

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