Pt<sup>II</sup> and Rh<sup>III</sup> Hydrocarbyl Complexes Bearing Coordinated Oxygen Atom Delivery Reagents

Webb, Joanna R.; Figg, Travis M.; Otten, Brooke M.; Cundari, Thomas R.; Gunnoe, T. Brent; Sabat, Michal

doi:10.1002/ejic.201300434

Cited by 9 publications

(14 citation statements)

References 61 publications

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“…The CH 3 –Rh–N aniline bond angle of complex 1 is 88.0(1)°. The Rh–CH 3 bond length of complex 1 is 2.063(3) Å, which is in close agreement with the Rh–CH 3 bond length of [( t bpy) 2 Rh(Me) 2 ][BAr′ 4 ] [2.089(9) Å] 23…”

Section: Resultssupporting

confidence: 78%

“…We have previously reported that the trifluoromethanesulfonate (OTf) ligand of [( t bpy) 2 Rh(Me)(OTf)][BAr′ 4 ] is labile and is substituted by H 2 O upon heating in THF to afford [( t bpy) 2 Rh(Me)(H 2 O)][BAr′ 4 ][OTf] 23. Likewise, the OTf ligand of [( t bpy) 2 Rh(Me)(OTf)][BAr′ 4 ] can be replaced by aniline to give [( t bpy) 2 Rh(Me)(NH 2 Ph)][BAr′ 4 ][OTf] ( 1 ) in 80 % isolated yield [Equation (1)].…”

Section: Resultsmentioning

confidence: 99%

“…The t bpy version of [(bpy) 2 Rh(Cl) 2 ]Cl was synthesized by following the published procedure 39. The complexes [( t bpy) 2 Rh(OTf) 2 ][OTf],16,39 [( t bpy) 2 Rh(Cl) 2 ][BAr′ 4 ],23 [( t bpy) 2 Rh(Me) 2 ][BAr′ 4 ],23 [( t bpy) 2 Rh(Me)(OTf)][BAr′ 4 ],23 and [(bpy) 2 Rh(py)(Cl)][PF 6 ]31 were prepared according to published procedures. All other reagents were purchased from commercial sources and used without further purification.…”

Section: Methodsmentioning

confidence: 99%

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Synthesis of Rh^III Anilido, Hydroxide, and Methoxide Complexes

et al. 2015

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The octahedral Rh III complexes [( t bpy) 2 Rh(XH) 2 ][OTf] 3 ( t bpy = 4,4Ј-di-tert-butyl-2,2Ј-bipyridyl; X = NHPh or OH; OTf = trifluoromethanesulfonate), [( t bpy) 2 Rh(X) 2 ][OTf] (X = NHPh or OH), [( t bpy) 2 Rh(NHPh)(NH 2 Ph)][OTf] 2 , [( t bpy) 2 Rh(Me)-(NH 2 Ph)][OTf][BArЈ 4 ] (BArЈ 4 = tetrakis[(3,5-bis-trifluoromethyl)phenyl]borate), [( t bpy) 2 Rh(Me)(NHPh)][BArЈ 4 ], [( t bpy) 2 Rh(OMe)(Cl)]Cl, and [(bpy)Rh(X) 2 ][PF 6 ] (bpy = 2,2Ј-[a] 1041bipyridyl; X = OH, OMe) have been synthesized and characterized by 1 H, 13 C{ 1 H}, and 19 F NMR spectroscopy, elemental analysis, or high-resolution mass spectrometry as well as single-crystal X-ray diffraction for some complexes. A comparison of the solid-state structural data for [( t bpy) 2 Rh(Me)-(NH 2 Ph)] 2+ , [( t bpy) 2 Rh(NH 2 Ph) 2 ] 3+ , [( t bpy) 2 Rh(NHPh) 2 ] + , and [( t bpy) 2 Rh(NHPh)(NH 2 Ph)] 2+ is included.

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Section: Resultssupporting

confidence: 78%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Synthesis of Rh^III Anilido, Hydroxide, and Methoxide Complexes

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“…Instead, OAT was believed to cause oxidative degradation of at least 20% of the iridium starting material 7. The results of these two thermolysis reactions are similar to what was observed in thermolysis reactions of platinum and rhodium compounds with coordinated pyridine-N-oxide ligands 15. Photolysis.…”

supporting

confidence: 81%

“…13 N-oxides also coordinate to platinum and rhodium compounds, generating stable models of intermediates proposed in oxyfunctionalization reactions. [14][15] A Rh(Cp*) complex with a coordinated iodosylbenzene derivative and an Ir(Cp*) compound with a coordinated pyridine-N-oxide are also known, but oxidation to form terminal metal-oxo complexes was not described. 10,16 Compounds with coordinated OAT reagents are relatively easy to handle and serve as well-defined precursors for oxygen atom transfer reactions.…”

Section: Introductionmentioning

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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Methyl Complexes of the Transition Metals

Campos

López‐Serrano

Peloso

et al. 2016

Chemistry A European J

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Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, i.e. based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition metal complexes containing M-CH3 fragments. Taking into account the impressive amount of data that are continuously provided by organometallic chemists in this area, this review is mainly focused on results of the last 5 years. After a panoramic overview on M-CH3 compounds of groups 3 to 11 which includes the most recent landmark findings in this area, two further sections are dedicated to methyl-bridged complexes and reactivity.

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Pt^II and Rh^III Hydrocarbyl Complexes Bearing Coordinated Oxygen Atom Delivery Reagents

Cited by 9 publications

References 61 publications

Synthesis of Rh^III Anilido, Hydroxide, and Methoxide Complexes

Synthesis of Rh^III Anilido, Hydroxide, and Methoxide Complexes

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

Methyl Complexes of the Transition Metals

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PtII and RhIII Hydrocarbyl Complexes Bearing Coordinated Oxygen Atom Delivery Reagents

Cited by 9 publications

References 61 publications

Synthesis of RhIII Anilido, Hydroxide, and Methoxide Complexes

Synthesis of RhIII Anilido, Hydroxide, and Methoxide Complexes

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

Methyl Complexes of the Transition Metals

Contact Info

Product

Resources

About

Pt^II and Rh^III Hydrocarbyl Complexes Bearing Coordinated Oxygen Atom Delivery Reagents

Synthesis of Rh^III Anilido, Hydroxide, and Methoxide Complexes

Synthesis of Rh^III Anilido, Hydroxide, and Methoxide Complexes

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