How to tame a palladium terminal oxo

Munz, Dominik

doi:10.1039/c7sc05034h

Cited by 26 publications

(14 citation statements)

References 150 publications

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“…As pointed out by a referee we noticed that such a breakdown of the conventional Lewis electron–pair model is not a unique phenomenon of group 11 oxygen compounds. One closely related example is the recently investigated oxygen-centered OHgF radical 39 , but also other transition metal terminal oxo complexes bearing terminal oxygen-centered radicals have been predicted 22 – 24 , 40 . Terminal oxygen radicals have also been found to occur in metal oxide clusters of early transition metals, when these metals are in their highest oxidation state.…”

Section: Discussionmentioning

confidence: 96%

Oxygen radical character in group 11 oxygen fluorides

Stüker

Kieninger

et al. 2018

Nat Commun

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Transition metal complexes bearing terminal oxido ligands are quite common, yet group 11 terminal oxo complexes remain elusive. Here we show that excited coinage metal atoms M (M = Au, Ag, Cu) react with OF2 to form hypofluorites FOMF and group 11 oxygen metal fluorides OMF2, OAuF and OAgF. These compounds have been characterized by IR matrix-isolation spectroscopy in conjunction with state-of-the-art quantum-chemical calculations. The oxygen fluorides are formed by photolysis of the initially prepared hypofluorites. The linear molecules OAgF and OAuF have a 3Σ − ground state with a biradical character. Two unpaired electrons are located mainly at the oxygen ligand in antibonding O−M π* orbitals. For the 2B2 ground state of the OMIIIF2 compounds only an O−M single bond arises and a significant spin-density contribution was found at the oxygen atom as well.

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Section: Discussionmentioning

confidence: 96%

Oxygen radical character in group 11 oxygen fluorides

Stüker

Kieninger

et al. 2018

Nat Commun

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“…We recently reported as eries of terminal iridium(IV/V) nitrido and iridium(III/IV/V) imido complexes,[ Ir(N)-(PNP)] n+ (PNP = N(CHCHP t Bu 2 ) 2 ; n = 0, 1) [11] and [Ir(N t Bu)-(PNP)] n+ (n = 0( 1), 1( 2), 2( 3); Figure 1). [12] Then eutral imide 1 represents an unprecedented iridium complex with an electronic triplet ground state and high imidyl N-radical character,which renders the {Ir(PNP)} platform attractive to examine electronic effects.Herein, we report the first isolable, open-shell iridium oxo complex, which was obtained upon hydrogen atom transfer (HAT) from an iridium(II) hydroxo precursor,and its reactivity with respect to oxo transfer.…”

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confidence: 99%

A Terminal Iridium Oxo Complex with a Triplet Ground State

et al. 2019

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Aterminal iridium oxocomplex with an open-shell (S = 1) ground state was isolated upon hydrogen atom transfer (HAT) from the respective iridium(II) hydroxide.E lectronic structure examinations support large spin delocalization to the oxygen atom. Selected oxot ransfer reactions indicate the ambiphilic reactivity of the iridium oxom oiety.C alorimetric and computational examinations of the HATrevealed ab ond dissociation free energy for the IrO À Hb ond that is sufficient for hydrogen atom abstraction towardsC À Hbonds and small contributions from entropya nd spin-orbit coupling to the HATthermochemistry.

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“…Following our computational predictions, [23,24] we reported recently the first example for a terminal imido complex of palladium (1). [25] This d 8 -configured nitrene complex is surprisingly stable owing to the strong ligand field, which is exerted by the ancillary cyclic (alkyl)(amino)carbene (CAAC) ligand.…”

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confidence: 54%

Carbon Dioxide Activation by a Palladium Terminal Imido Complex

et al. 2019

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We recently reported the first example of a palladium(ii) terminal imido complex. We proposed that this complex features exceptional high nucleophilicity at the nitrogen atom and a peculiar zwitterionic electronic structure with an anti-bonding highest-occupied molecular orbital (HOMO). This complex swiftly activated moderately acidic CH, OH, and NH bonds and also reacted with dihydrogen. However, unambiguous nucleophilic reactivity with substrates not featuring a hydrogen atom could not be observed. Herein, we now show that this nucleophilic complex also reacts with CO2 to give a ring-strained four-membered palladium(ii) carbamate complex. Remarkably, the same product is obtained in the reaction of the related bisamido complex, albeit at a slower reaction rate. Density functional theory calculations indicate that the addition of CO2 does not proceed via initial 1,2-addition across the Pd–N bond, but instead through nucleophilic attack by the imido (amido respectively) nitrogen atom.

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How to tame a palladium terminal oxo

Abstract: The isolation of terminal oxo complexes of the late transition metals promises new avenues in oxidation catalysis like the selective and catalytic hydroxylation of unreactive CH bonds, the activation of water, or the upgrading of olefins.

Cited by 26 publications

References 150 publications

Oxygen radical character in group 11 oxygen fluorides

Oxygen radical character in group 11 oxygen fluorides

A Terminal Iridium Oxo Complex with a Triplet Ground State

Carbon Dioxide Activation by a Palladium Terminal Imido Complex

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