Facile oxidative addition of water at iridium: reactivity of trans-[Ir(4-C5NF4)(H)(OH)(PiPr3)2] towards CO2 and NH3

Kläring, Paul; Pahl, S.; Braun, Thomas; Penner, Anna

doi:10.1039/c1dt10173k

Cited by 44 publications

(25 citation statements)

References 68 publications

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“…The situation is quite different in bridging parent amido complexes, in which the lone electronic pair is usually tightly bounded in a dative fashion to a second metal 13. 16a, b, f, 18, 24 In this context, a significant contribution has been recently reported dealing with the role of [Ir‐NH 2 ‐Ir] linkages in catalytic transfer hydrogenation, enlightening a novel binuclear, outer‐sphere Noyori‐like mechanism, in which the NH 2 groups behave as non‐innocent ligands playing a key role in alcohol dehydrogenation and imido formation 25…”

Section: Introductionmentioning

confidence: 99%

Terminal and Bridging Parent Amido 1,5‐Cyclooctadiene Complexes of Rhodium and Iridium

Mena

Jaseer

Garcı́a-Orduña

et al. 2013

Chemistry A European J

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The ready availability of rare parent amido d(8) complexes of the type [{M(μ-NH2)(cod)}2] (M=Rh (1), Ir (2); cod=1,5-cyclooctadiene) through the direct use of gaseous ammonia has allowed the study of their reactivity. Both complexes 1 and 2 exchanged the di-olefines by carbon monoxide to give the dinuclear tetracarbonyl derivatives [{M(μ-NH2)(CO)2}2 ] (M=Rh or Ir). The diiridium(I) complex 2 reacted with chloroalkanes such as CH2Cl2 or CHCl3, giving the diiridium(II) products [(Cl)(cod)Ir(μ-NH2)2Ir(cod)(R)] (R=CH2Cl or CHCl2) as a result of a two-center oxidative addition and concomitant metal-metal bond formation. However, reaction with ClCH2CH2Cl afforded the symmetrical adduct [{Ir(μ-NH2)(Cl)(cod)}2] upon release of ethylene. We found that the rhodium complex 1 exchanged the di-olefines stepwise upon addition of selected phosphanes (PPh3, PMePh2, PMe2Ph) without splitting of the amido bridges, allowing the detection of mixed COD/phosphane dinuclear complexes [(cod)Rh(μ-NH2)2Rh(PR3)2], and finally the isolation of the respective tetraphosphanes [{Rh(μ-NH2)(PR3)2}2]. On the other hand, the iridium complex 2 reacted with PMe2 Ph by splitting the amido bridges and leading to the very rare terminal amido complex [Ir(cod)(NH2)(PMePh2)2]. This compound was found to be very reactive towards traces of water, giving the more stable terminal hydroxo complex [Ir(cod)(OH)(PMePh2)2]. The heterocyclic carbene IPr (IPr=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) also split the amido bridges in complexes 1 and 2, allowing in the case of iridium to characterize in situ the terminal amido complex [Ir(cod)(IPr)(NH2)]. However, when rhodium was involved, the known hydroxo complex [Rh(cod)(IPr)(OH)] was isolated as final product. On the other hand, we tested complexes 1 and 2 as catalysts in the transfer hydrogenation of acetophenone with iPrOH without the use of any base or in the presence of Cs2CO3, finding that the iridium complex 2 is more active than the rhodium analogue 1.

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Section: Introductionmentioning

confidence: 99%

Terminal and Bridging Parent Amido 1,5‐Cyclooctadiene Complexes of Rhodium and Iridium

Mena

Jaseer

Garcı́a-Orduña

et al. 2013

Chemistry A European J

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“…Milstein and coworkers described the clean formation of hydride-hydroxide complexes from [Ir I (PMe 3 ) 4 ] [PF 6 ] (26) and Ir I Cl(PMe 3 ) 3 (27), respectively (Milstein et al 1986, Blum and. Other more recent examples include oxidative addition with prior dissociation of a stabilising ligand as seen in the systems Ir I [PiPr 2 (methylene-1-adamantyl)] 2 (H)(h 1 -N 2 ) (29) (Millard et al 2010) and Ir I (C 5 NF 4 )(PiPr 3 ) 2 (h 2 -C 2 H 4 ) (30) (Kläring et al 2011). The latter compound forms a rare example of a 16-electron iridium hydride-hydroxide (31).…”

Section: Oxidative Additionmentioning

confidence: 98%

Organometallic water splitting – from coordination chemistry to catalysis

Klahn

Beweries

2014

Reviews in Inorganic Chemistry

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AbstractThis review gives an overview on the recent developments in the field of coordination chemistry of water at transition metal centres, which could give implications for a better understanding of the elementary steps of light-driven overall water splitting. Additionally, selected examples for homogeneous catalyst systems that are capable of producing hydrogen and/or oxygen from water are presented, focussing on the mechanistic aspects of water reduction and water oxidation.

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“…1 All volatiles were removed in vacuo and the residue was washed three times with n-hexane (5 mL). The obtained yellow residue was extracted three times with toluene (10 mL) and the filtrate was concentrated to 5 mL and left at À30 8C for three days to afford a yellow crystalline product, which was separated from the mother liquor by filtration and dried in vacuo for 30 Compound 17: A solution of 8 (30.4 mg, 0.05 mmol) in toluene (10 mL) at À25 8C was placed in a Schlenk tube and degassed by a freeze-pump-thaw cycle. The reaction vessel was charged with NH 3 of normal pressure.…”

Section: Experimental Section General Considerationsmentioning

confidence: 99%

A Donor‐Stabilized Zwitterionic “Half‐Parent” Phosphasilene and Its Unusual Reactivity towards Small Molecules

Hansen

Szilvási

Blom

et al. 2014

Chemistry A European J

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The stabilization of the labile, zwitterionic "half-parent" phosphasilene 4 L'Si=PH (L'=CH[(C=CH2)CMe(NAr)2]; Ar=2,6-iPr2C6H3) could now be accomplished by coordination with two different donor ligands (4-dimethylaminopyridine (DMAP) and 1,3,4,5-tetramethylimidazol-2-ylidene), affording the adducts 8 and 9, respectively. The DMAP-stabilized zwitterionic "half-parent" phosphasilene 8 is capable of transferring the elusive parent phosphinidene moiety (:PH) to an unsaturated organic substrate, in analogy to the "free" phosphasilene 4. Furthermore, compounds 4 and 8 show an unusual reactivity of the Si=P moiety towards small molecules. They are capable of adding dimethylzinc and of activating the S-H bonds in H2S and the N-H bonds in ammonia and several organoamines. Interestingly, the DMAP donor ligand of 8 has the propensity to act as a leaving group at the phosphasilene during the reaction. Accordingly, treatment of 8 with H2S affords, under liberation of DMAP, the unprecedented thiosilanoic phosphane LSi=S(PH2) 16 (L=HC(CMe[2,6-iPr2C6H3N])2). Compounds 4 and 8 react with ammonia both affording L'Si(NH2)PH2 17, respectively. In addition, the reaction of 8 with isoproylamine, p-toluidine, and pentafluorophenylhydrazine lead to the corresponding phosphanylsilanes L'Si(PH2)NHR (R=iPr 18 a; R=C6H5-CH3 18 b, R=NH(C6F5) 18 c), respectively.

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Facile oxidative addition of water at iridium: reactivity of trans-[Ir(4-C5NF4)(H)(OH)(PiPr3)2] towards CO2 and NH3

Cited by 44 publications

References 68 publications

Terminal and Bridging Parent Amido 1,5‐Cyclooctadiene Complexes of Rhodium and Iridium

Terminal and Bridging Parent Amido 1,5‐Cyclooctadiene Complexes of Rhodium and Iridium

Organometallic water splitting – from coordination chemistry to catalysis

A Donor‐Stabilized Zwitterionic “Half‐Parent” Phosphasilene and Its Unusual Reactivity towards Small Molecules

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