Dataset Information

A Cyclometalated NHC Iridium Complex Bearing a Cationic (η⁵ -Cyclopentadienyl)(η⁶ -phenyl)iron Backbone*.

ABSTRACT: Nucleophilic substitution of [(η⁵ -cyclopentadienyl)(η⁶ -chlorobenzene)iron(II)] hexafluorophosphate with sodium imidazolate resulted in the formation of [(η⁵ -cyclopentadienyl)(η⁶ -phenyl)iron(II)]imidazole hexafluorophosphate. The corresponding dicationic imidazolium salt, which was obtained by treating this imidazole precursor with methyl iodide, underwent cyclometallation with bis[dichlorido(η⁵ -1,2,3,4,5-pentamethylcyclopentadienyl]iridium(III) in the presence of triethyl amine. The resulting bimetallic iridium(III) complex is the first example of an NHC complex bearing a cationic and cyclometallated [(η⁵ -cyclopentadienyl)(η⁶ -phenyl)iron(II)]⁺ substituent. As its iron(II) precursors, the bimetallic iridium(III) complex was fully characterized by means of spectroscopy, elemental analysis and single crystal X-ray diffraction. In addition, it was investigated in a catalytic study, wherein it showed high activity in transfer hydrogenation compared to its neutral analogue having a simple phenyl instead of a cationic [(η⁵ -cyclopentadienyl)(η⁶ -phenyl)iron(II)]⁺ unit at the NHC ligand.

SUBMITTER: Malchau C

PROVIDER: S-EPMC8596692 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

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Publications

A Cyclometalated NHC Iridium Complex Bearing a Cationic (η5 -Cyclopentadienyl)(η6 -phenyl)iron Backbone*.

Malchau Christian C Milbert Tom T Eger Tobias R TR Fries Daniela V DV Pape Pascal J PJ Oelkers Benjamin B Sun Yu Y Becker Sabine S Prosenc Marc H MH Niedner-Schatteburg Gereon G Thiel Werner R WR

Chemistry (Weinheim an der Bergstrasse, Germany) 20211005 61

Nucleophilic substitution of [(η5 -cyclopentadienyl)(η6 -chlorobenzene)iron(II)] hexafluorophosphate with sodium imidazolate resulted in the formation of [(η5 -cyclopentadienyl)(η6 -phenyl)iron(II)]imidazole hexafluorophosphate. The corresponding dicationic imidazolium salt, which was obtained by treating this imidazole precursor with methyl iodide, underwent cyclometallation with bis[dichlorido(η5 -1,2,3,4,5-pentamethylcyclopentadienyl]irid ...[more]

PMID: 34432336

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Project description:When reacted in dry, degassed toluene, [Ir(COD)Cl]2 (COD = cyclo-octa-1,5-diene) and 2 equivalents of 2-(di-tert-butyl-phosphinito)anthra-quinone (tBuPOAQH) were found to form a unique tri-iridium compound consisting of one monoanionic dinuclear tri-μ-chlorido complex bearing one bidentate tBuPOAQ ligand per iridium, which was charge-balanced by an outer sphere [Ir(toluene)(COD)]+ ion, the structure of which has not previously been reported. This product, which is a toluene solvate, namely, (η2:η2-cyclo-octa-1,5-diene)(η6-toluene)-iridium(I) tri-μ-chlorido-bis-({3-[(di-tert-butyl-phosphan-yl)-oxy]-9,10-dioxoanthracen-2-yl}hydridoiridium(III)) toluene monosolvate, [Ir(C7H8)(C8H12)][Ir2H2(C22H24O3P)2Cl3]·C7H8 or [Ir(toluene)(COD)][Ir(κ-P,C-tBuPOAQ)(H)]2(μ-Cl)3]·toluene, formed as small orange platelets at room temperature, crystallizing in the triclinic space group P. The cation and anion are linked via weak C-H⋯O inter-actions. The stronger inter-molecular attractions are likely the offset parallel π-π inter-actions, which occur between the toluene ligands of pairs of inverted cations and between pairs of inverted anthra-quinone moieties, the latter of which are capped by toluene solvate mol-ecules, making for π-stacks of four mol-ecules each. The related ligand, 2-(di-tert-butyl-phosphinometh-yl)-anthra-quinone (tBuPCAQH), did not form crystals suitable for X-ray diffraction under analogous reaction conditions. However, when the reaction was conducted in chloro-form, yellow needles readily formed following addition of 1 atm of carbon monoxide. Diffraction studies revealed a neutral, dinuclear, di-μ-chlorido complex, di-μ-chlorido-bis-(carbon-yl{3-[(di-tert-butyl-phosphan-yl)-oxy]-9,10-dioxoanthracen-2-yl}hydridoiridium(I)), [Ir2H2(C23H26O2P)2Cl2(CO)2] or [Ir(κ-P,C-tBuPCAQ)(H)(CO)(μ-Cl)]2, Ir2C48H54Cl2O6P2, again crystallizing in space group P. Offset parallel π-π inter-actions between anthra-quinone groups of adjacent mol-ecules link the mol-ecules in one dimension.

Dataset Information

A Cyclometalated NHC Iridium Complex Bearing a Cationic (η⁵ -Cyclopentadienyl)(η⁶ -phenyl)iron Backbone*.

Publications

A Cyclometalated NHC Iridium Complex Bearing a Cationic (η<sup>5</sup> -Cyclopentadienyl)(η<sup>6</sup> -phenyl)iron Backbone*.

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