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

Sau, Yiu‐Keung; Yi, Xiao‐Yi; Chan, Ka Man; Lai, Chun-Sing; Williams, Ian D.; Leung, Wa‐Hung

doi:10.1016/j.jorganchem.2010.02.002

Cited by 52 publications

(23 citation statements)

References 22 publications

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“…This suggests that the (S Ru , S S ) and (R Ru , R S ) isomers observed in the crystal are retained in solution. Similar stereoselectivity was recently reported for the iridium(III) complex [(η 5 -C 5 Me 5 )Ir(η 2 -ppy-S-p-tol)(H 2 O)](OTf) 2 (Sau et al, 2010), in which the structure of the chelate ring is analogous to that for btppy in (I).…”

supporting

confidence: 84%

(η⁶-Benzene){2-[2-(tert-butylsulfanyl)phenyl]pyridine-κ²N,S}chloridoruthenium(II) hexafluoridophosphate

2010

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In the title compound, [RuCl(C6H6)(C15H17NS)]PF6, the cation adopts a three-legged piano-stool structure around the Ru(II) atom with an η6-benzene ligand, a chloride ligand and a 2-[2-(tert-butylsulfanyl)phenyl]pyridine (btppy) ligand. The btppy ligand acts as a N,S-bidentate ligand, forming a six-membered ring, which has an envelope conformation. The S—Ru—N bite angle is 86.76 (9)°, and the dihedral angle between the pyridine and benzene rings in btppy is 39.8 (2)°. The unit cell contains two pairs of racemic diastereomers with (S Ru,S S) and (R Ru,R S) configurations, in which the tert-butyl group on the coordinated S atom is distant from the η6-benzene ligand.

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supporting

confidence: 84%

(η⁶-Benzene){2-[2-(tert-butylsulfanyl)phenyl]pyridine-κ²N,S}chloridoruthenium(II) hexafluoridophosphate

2010

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“…14, Rh 1 -N 1 2.1108 16 [Ir(Cp*)(phpy)(NCCH 3 )] + has been documented. 22 In addition, oxygen atom insertion into the rhodium-carbon bond of coordinated phpy at a Rh(Cp*) complex has been observed. 16 Oxygen atom insertion does not occur in the thermolysis reaction presented here.…”

Section: Resultsmentioning

confidence: 99%

“…The major product was identified as the pyridine adduct, [Ir(Cp*)(phpy)(pyridine)] + , which was formed in 35% yield. The identity of the product was verified by comparison to a known sample of [Ir(Cp*)(phpy)(pyridine)] + , which was generated in situ by adding pyridine to the acetonitrile adduct, [Ir(Cp*)(phpy)(NCCH 3 )] + 22. An additional 43% of the iridium species might be accounted for by summing the integrals of two resonances in the alkyl region (the resonances might correspond to -CH 3 groups of the Cp* ligand), but these minor species could not be identified because the 1 H NMR spectrum was complex.…”

mentioning

confidence: 99%

Half-sandwich Rh(Cp) and Ir(Cp) complexes with oxygen atom transfer reagents as ligands

Turlington

White

Brookhart

et al. 2015

Journal of Organometallic Chemistry

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We are grateful to Professor Michael Mingos, a superb chemist and a congenial host, for his many outstanding contributions to inorganic chemistry. ABSTRACT. Rhodium(Cp*) and iridium(Cp*) complexes with bidentate ligands and a coordinated oxygen atom transfer reagent as the final ligand in the d 6 coordination sphere are described (Cp* = η 5-pentamethylcyclopentadienyl). A Rh(Cp*) cation with a pyridyl-benzamide bidentate ligand resistant to insertion and a coordinated oxygen atom transfer reagent, 2-tertbutylsulfonyliodosylbenzene (sPhIO), was isolated in the solid state. In anhydrous solution, the sPhIO ligand was reduced over 24 hours, and a solvent-stabilized, 16-electron rhodium complex was formed. Oxygen atom transfer either led to unobserved oxidative degradation of a small fraction of the rhodium species, or formed the iodoxyarene, sPhIO 2 , via a known disproportionation reaction. The reduced oxidant, sPhI, did not coordinate to rhodium, but the 16-electron cation was readily trapped by water. The organometallic Ir(Cp*) backbone with cyclometalated 2-phenylpyridine (phpy) formed stable complexes with the mild oxygen atom 2 transfer reagents pyridine-N-oxide and 4-methoxy-pyridine-N-oxide. Oxygen atom transfer from the coordinated N-oxides was induced by thermolysis or photolysis and initially led to decomposition of a small fraction of the samples. The liberated pyridine derivatives displaced coordinated N-oxides and somewhat limited decomposition of the Ir(Cp*)(phpy) backbone. Neither oxygen atom insertion into the metal-carbon bond of coordinated phpy nor metal-oxo complexes were observed.

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“…Although the exact mechanism of this reaction remains elusive,o nt he basis of the above observations and the previous work, aplausible mechanism is illustrated to account for the unprecedented silver-catalyzed pyrimidinedione synthesis from cyclic oximes and isocyanides.A sd epicted in Scheme 9, the cyclic oxime 1 may tautomerize to the isoxazol-5(2H)-one 1' ', [24] which then reacts with the silver(I) salt by using pyridine as ab ase to generate the silver complex A. Subsequent isocyanidei nsertion affords the intermediate B, followed by ring opening to give rise to the silver-nitrene species C. [25] After intramolecular nitrene insertion into the CÀAg bond, [26] the species D is delivered, and then undergoes protonation to furnish the imidate E.The compound E could undergo ring opening [15] to produce the species F,w hich is then converted into the desired product 3 through intramolecular CÀNbond formation. Note that another role of the pyridine might be to enhance the solubility of the silver salt by virtue of its good coordination ability to the silver salt.…”

Section: Angewandte Chemiementioning

confidence: 99%

Atom‐Economic Silver‐Catalyzed Difunctionalization of the Isocyano Group with Cyclic Oximes: Towards Pyrimidinediones

et al. 2018

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An unprecedented silver-catalyzed difunctionalization of the isocyano group with cyclic oximes is described. This method allows efficient and atom-economic assembly of avast arrayo fs tructurally novel and interesting pyrimidinediones, and tolerates arange of functionalities.The resulting products can be easily converted into some useful compounds.F urthermore,t he method can also be applied for the late-stage modification of af ew biologically active molecules. Scheme 1. Functionalization of the isocyanogroup.

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

Cited by 52 publications

References 22 publications

(η⁶-Benzene){2-[2-(tert-butylsulfanyl)phenyl]pyridine-κ²N,S}chloridoruthenium(II) hexafluoridophosphate

(η⁶-Benzene){2-[2-(tert-butylsulfanyl)phenyl]pyridine-κ²N,S}chloridoruthenium(II) hexafluoridophosphate

Half-sandwich Rh(Cp) and Ir(Cp) complexes with oxygen atom transfer reagents as ligands

Atom‐Economic Silver‐Catalyzed Difunctionalization of the Isocyano Group with Cyclic Oximes: Towards Pyrimidinediones

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

Cited by 52 publications

References 22 publications

(η6-Benzene){2-[2-(tert-butylsulfanyl)phenyl]pyridine-κ2N,S}chloridoruthenium(II) hexafluoridophosphate

(η6-Benzene){2-[2-(tert-butylsulfanyl)phenyl]pyridine-κ2N,S}chloridoruthenium(II) hexafluoridophosphate

Half-sandwich Rh(Cp*) and Ir(Cp*) complexes with oxygen atom transfer reagents as ligands

Atom‐Economic Silver‐Catalyzed Difunctionalization of the Isocyano Group with Cyclic Oximes: Towards Pyrimidinediones

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Product

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(η⁶-Benzene){2-[2-(tert-butylsulfanyl)phenyl]pyridine-κ²N,S}chloridoruthenium(II) hexafluoridophosphate

(η⁶-Benzene){2-[2-(tert-butylsulfanyl)phenyl]pyridine-κ²N,S}chloridoruthenium(II) hexafluoridophosphate

Half-sandwich Rh(Cp) and Ir(Cp) complexes with oxygen atom transfer reagents as ligands