Structural diversity and solution behavior of low-valent iridium complexes bearing 1,4-diazabutadiene ligands

Langer, Jens; Görls, Helmar

doi:10.1016/j.inoche.2011.06.022

Cited by 5 publications

(6 citation statements)

References 28 publications

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“…Overall, the DFT calculations and XANES spectra suggest that the rhodium and iridium atoms in 2 and 3 are characterized by the formal oxidation state +I. The low electron density at the metal centers revealed by the IR spectra is apparently due to a certain degree of π‐back‐bonding to the diimine ligands 14. This bonding scheme is also compatible with the structural features determined by X‐ray crystallography.…”

Section: Resultssupporting

confidence: 73%

“…The C=N bond lengths in 3 are 1.302(6) and 1.336(6) Å, whereas the bond lengths found for the cationic complex [Ir(CO) 2 {ArN=C(H)C(H)=NAr}][BF 4 ] [Ar = 2,6‐ i Pr 2 C 6 H 3 , 1.270(2) and 1.279(3) Å] are shorter 13b. The C1–C2 bond length in 3 of 1.417(7) Å is identical to the corresponding C–C bond length in [Ir(Cl){MesN=C(H)C(H)=NMes}(coe)] [1.394(7) Å] 14…”

Section: Resultsmentioning

confidence: 95%

“…The corresponding doublets for [Ir(Cl){MesN=C(H)C(H)=NMes}(CN t Bu)] ( 3 ) are found at δ = 10.94 and 8.07 ppm ( 3 J H,H = 1.0 Hz). For the complex [Ir(Cl){MesN=C(H)C(H)=NMes}(coe)] (coe = cyclooctene), two doublets at δ = 11.76 and 8.93 ppm ( 3 J H,H = 0.8 Hz) were observed 14. The 13 C NMR spectrum of 1 shows one broad signal at δ = 127.16 ppm ( 2 : δ = 128.53 ppm) for the Rh C N t Bu carbon atom.…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…The α‐dialdimine iridium complexes [Ir(Cl){MesN=C(H)C(H)=NMes}(coe)] (coe = cyclooctene) and [Ir(Cl){MesN=C(H)C(H)=NMes} 2 ] revealed a certain degree of π‐back‐bonding to the diimine ligand 14. The structural data, which were determined by X‐ray crystallography, suggest the presence of mono‐reduced diimine ligands 14. Tejel et al reported studies on the deprotonation reactions of the bis(picolyl)amine ligand [bpa = HN(CH 2 ‐2‐NC 5 H 4 ) 2 ] in the complex [Ir(bpa)(cod)][PF 6 ] (cod = cyclooctadiene) with KO t Bu to give the doubly deprotonated compound K[Ir(bpa‐2H)(cod)] 15.…”

Section: Introductionmentioning

confidence: 99%

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α‐Dialdimine Complexes of Rhodium(I) and Iridium(I): Their Reactivity with Dioxygen and Dihydrogen

et al. 2013

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The rhodium(I) and iridium(I) complexes [M(Cl){ArN=C(H)-C(H)=NAr}(CNtBu)] (1: M = Rh, Ar = 2,6-iPr 2 C 6 H 3 ; 2: M = Rh, Ar = Mes; 3: M = Ir, Ar = Mes; Mes = 2,4,6-Me 3 C 6 H 2 ) have been prepared by the reaction of [M(μ-Cl)(coe) 2 ] 2 (M = Rh, Ir; coe = cyclooctene) with the α-dialdimines ArN=C(H)-C(H)=NAr (Ar = 2,6-iPr 2 C 6 H 3 , Mes) in thf, followed by the addition of CNtBu. XANES spectra and DFT calculations on 2 and 3 suggest an oxidation state +I at the metal centers. Treatment of the complexes 2 and 3 with O 2 or 18 O 2 gave the peroxido complexes [M(Cl)(O 2 ){MesN=C(H)C(H)=NMes}-[a] Humboldt-

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Section: Resultssupporting

confidence: 73%

Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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α‐Dialdimine Complexes of Rhodium(I) and Iridium(I): Their Reactivity with Dioxygen and Dihydrogen

et al. 2013

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Heteroleptic 1,4‐Diazabutadiene Complexes of Ruthenium: Synthesis, Characterization and Utilization in Catalytic Transfer Hydrogenation

2020

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Reaction of [Ru(trpy)Cl3] with 1,4‐diazabutadienes (p‐RC6H4N=C(H)‐(H)C=NC6H4R‐p; R = OCH3, CH3, H and Cl; abbreviated as L‐R) in refluxing ethanol in the presence of triethylamine has afforded a family of complexes, isolated as perchlorate salts, of type [Ru(trpy)(L‐R)Cl]ClO4 [depicted as complexes 1 (R = OCH3), 2 (R = CH3), 3 (R = H) and 4 (R = Cl)]. Crystal structures of complexes 1, 2 and 4 have been determined, and structure of complex 3 has been optimized by DFT method. The 1,4‐diazabutadiene ligand in each complex is bound to ruthenium as a N,N‐donor forming five‐membered chelate. Complexes 1–4 catalyze transfer hydrogenation of aryl aldehydes to the corresponding alcohols with high (ca. 106) TON. They are also found to catalyze transfer hydrogenation of aryl ketones to corresponding secondary alcohols, but with much less efficiency. Catalytic transfer hydrogenation of nitroarenes to the corresponding amines has also been achieved.

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Copper complexes of 1,4-diazabutadiene ligands: Tuning of metal oxidation state and, application in catalytic C-C and C-N bond formation

Mukherjee

Basu

Bhattacharya

2020

Inorganica Chimica Acta

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Structural diversity and solution behavior of low-valent iridium complexes bearing 1,4-diazabutadiene ligands

Cited by 5 publications

References 28 publications

α‐Dialdimine Complexes of Rhodium(I) and Iridium(I): Their Reactivity with Dioxygen and Dihydrogen

α‐Dialdimine Complexes of Rhodium(I) and Iridium(I): Their Reactivity with Dioxygen and Dihydrogen

Heteroleptic 1,4‐Diazabutadiene Complexes of Ruthenium: Synthesis, Characterization and Utilization in Catalytic Transfer Hydrogenation

Copper complexes of 1,4-diazabutadiene ligands: Tuning of metal oxidation state and, application in catalytic C-C and C-N bond formation

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