Steric Manipulation of the Reductive Reactivity of Ytterbocenes toward 2-(((2,6-Diisopropylphenyl)imino)methyl)pyridine:  Insertion of the NC Bond into the Yb−Indenyl Bond or Oxidative Cleavage of the η5 Yb−Cp (Cp = C13H9, Cp*) Bond

Trifonov, Alexander A.; Федорова, Э. А.; Borovkov, Ivan A.; Fukin, Georgy K.; Баранов, Е. В.; Larionova, and Joulia; Druzhkov, N. O.

doi:10.1021/om070073s

Cited by 43 publications

(35 citation statements)

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“…[6] Numerous examples of coordination compounds containing the neutral closed-shell form (L 0 ) have been reported, [7] some of which display catalytic activity. [8] However, those incorporating the monoanionic radical form (LC À ) are restricted to a few first-row transition metals [9] and lanthanides, [10] while complexes with the closed-shell 2 e Àreduced dianionic form (L 2À ) are extremely rare. [9a, 11] We recently reported a unique anionic iridium(I) complex containing the dianionic (bpaÀ2 H) 2À ligand, [12] which is the 2 e À -reduced form of the a-iminopyridine ligand bpi (Scheme 1).…”

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confidence: 99%

Developing Synthetic Approaches with Non‐Innocent Metalloligands: Easy Access to Ir^I/Pd⁰ and Ir^I/Pd⁰/Ir^I Cores

et al. 2011

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Guilty as charged is the verdict for anionic Ir complex [Ir(bpa−2 H)(cod)]− in its reactions with PdII compounds. The net transfer of two electrons from the Ir complex to Pd allows easy preparation of di‐ and trinuclear π‐imine‐coordinated Pd0 compounds such as [{Ir(PyCH2NCHPy)(cod)}2Pd] (see picture; C white, Ir red, N blue, Pd yellow). bpa−2 H: doubly deprotonated form of N,N‐bis(2‐picolyl)amine (bpa); cod: 1,5‐cyclooctadiene.

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confidence: 99%

Developing Synthetic Approaches with Non‐Innocent Metalloligands: Easy Access to Ir^I/Pd⁰ and Ir^I/Pd⁰/Ir^I Cores

et al. 2011

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“…The a-iminopyridine N-2,6-diisopropylphenylimino-2-pyridine (IPy) has also been introduced in lanthanide chemistry. [33,34] In this context, a potassium derivative of the monoanionic form of a-iminopyridine was prepared in situ, but not further characterized.[34] The doubly reduced dianion has only been observed in two magnesium complexes so far. [35] In contrast, the reaction of "GaI" with a-iminopyridine leads to reductive coupling of the coordinated ligand to give neutral diamido-digallium complexes.…”

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confidence: 99%

Sodium and Potassium Salts of Mono‐ and Dianionic α‐Iminopyridines

Nayek

Arleth

Trapp

et al. 2011

Chemistry A European J

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[a] a-Diimine (1,4-diaza-1,3-butadiene) ligands are well established in main-group, transition-metal, and lanthanide chemistry. [1][2][3][4][5][6][7] Beside their application as ligands for latetransition-metal complexes, which can function as active and selective catalysts for a-olefin polymerization, [8] a-diimine and related ligands are of special interest due to their ability to undergo redox chemistry.[9] They have frequently been described as "non-innocent" ligands. [10][11][12] For example, in lanthanide chemistry, it has been found that the formal oxidation state of Eu [13] and Yb [14] depends on the nature of the substituents on the a-diimine ligand and on the ligand on the metal center. Thus, in both cases, the a-diimine acts either as neutral ligand or as radical anion. Reduction of adiimines, using either alkali metals or electrochemical methods, leads in each case to the corresponding radical anions [15][16][17][18] and eventually to diamagnetic dianions, [17][18][19][20][21][22][23][24] albeit at much more negative potentials. In contrast to the well-established chemistry of a-diimines, the related a-iminopyridines are much less investigated. The three different redox states of a-iminopyridines are shown in Scheme 1. The neutral system L 0 has been extensively used as ligand for late transition metals. [4,[25][26][27][28][29] Only recently, the monoanion LC À and the doubly reduced dianion L 2À were investigated as ligands in more detail. Recent reports showed a series of bis(a-iminopyridine)-metal complexes featuring aluminum [30] and the first-row transition ions (Cr, Mn, Fe, Co, Ni, and Zn) [31,32] with the monoanionic, and thus paramagnetic p-radical form of the ligand in coordination complexes. The a-iminopyridine N-2,6-diisopropylphenylimino-2-pyridine (IPy) has also been introduced in lanthanide chemistry. [33,34] In this context, a potassium derivative of the monoanionic form of a-iminopyridine was prepared in situ, but not further characterized.[34] The doubly reduced dianion has only been observed in two magnesium complexes so far. [35] In contrast, the reaction of "GaI" with a-iminopyridine leads to reductive coupling of the coordinated ligand to give neutral diamido-digallium complexes. [36] Based on this information, we were interested in a comprehensive study of the properties of the alkali metal salts of the monoanionic p-radical and the doubly reduced dianion of a-iminopyridine in solution and in the solid state. We report here the synthesis, characterization and magnetic properties of sodium and potassium salts of the mono-and dianionic a-iminopyridines.N-2,6-Diisopropylphenylimino-2-pyridine (IPy) was prepared according to literature procedures.[37] As a first entry point, we examined the electrochemical properties of IPy using cyclic voltammetry at room temperature in THF. As can be seen from Figure 1, we detected a quasi-reversible one-electron reduction process centered at E 0 1=2 = À2.57 V (vs. the ferrocene/ferrocenium couple, Fc/Fc + ), with a peakto-peak separation of 15...

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“…The ligand induced metal cleavage from Cp ring was unambiguously established [6,7]. However, the similar cleavage of indenyl ring is rare [27]. At present we still cannot explain how the cleavage process takes place.…”

Section: 2mentioning

confidence: 94%

Synthesis and reactivity of 2-(tert-butylcyclopentadienyl)-indenyl dinuclear ruthenium complex [η5:η5-(tBuC5H3)(C9H6)]Ru2(CO)4: Halogen induced Ru cleavage from indenyl ring

Li¹,

Tan²,

Xu³

et al. 2009

Journal of Organometallic Chemistry

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Steric Manipulation of the Reductive Reactivity of Ytterbocenes toward 2-(((2,6-Diisopropylphenyl)imino)methyl)pyridine: Insertion of the NC Bond into the Yb−Indenyl Bond or Oxidative Cleavage of the η⁵ Yb−Cp (Cp = C₁₃H₉, Cp*) Bond

Cited by 43 publications

References 16 publications

Developing Synthetic Approaches with Non‐Innocent Metalloligands: Easy Access to Ir^I/Pd⁰ and Ir^I/Pd⁰/Ir^I Cores

Developing Synthetic Approaches with Non‐Innocent Metalloligands: Easy Access to Ir^I/Pd⁰ and Ir^I/Pd⁰/Ir^I Cores

Sodium and Potassium Salts of Mono‐ and Dianionic α‐Iminopyridines

Synthesis and reactivity of 2-(tert-butylcyclopentadienyl)-indenyl dinuclear ruthenium complex [η5:η5-(tBuC5H3)(C9H6)]Ru2(CO)4: Halogen induced Ru cleavage from indenyl ring

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Steric Manipulation of the Reductive Reactivity of Ytterbocenes toward 2-(((2,6-Diisopropylphenyl)imino)methyl)pyridine: Insertion of the NC Bond into the Yb−Indenyl Bond or Oxidative Cleavage of the η5 Yb−Cp (Cp = C13H9, Cp*) Bond

Cited by 43 publications

References 16 publications

Developing Synthetic Approaches with Non‐Innocent Metalloligands: Easy Access to IrI/Pd0 and IrI/Pd0/IrI Cores

Developing Synthetic Approaches with Non‐Innocent Metalloligands: Easy Access to IrI/Pd0 and IrI/Pd0/IrI Cores

Sodium and Potassium Salts of Mono‐ and Dianionic α‐Iminopyridines

Synthesis and reactivity of 2-(tert-butylcyclopentadienyl)-indenyl dinuclear ruthenium complex [η5:η5-(tBuC5H3)(C9H6)]Ru2(CO)4: Halogen induced Ru cleavage from indenyl ring

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Steric Manipulation of the Reductive Reactivity of Ytterbocenes toward 2-(((2,6-Diisopropylphenyl)imino)methyl)pyridine: Insertion of the NC Bond into the Yb−Indenyl Bond or Oxidative Cleavage of the η⁵ Yb−Cp (Cp = C₁₃H₉, Cp*) Bond

Developing Synthetic Approaches with Non‐Innocent Metalloligands: Easy Access to Ir^I/Pd⁰ and Ir^I/Pd⁰/Ir^I Cores

Developing Synthetic Approaches with Non‐Innocent Metalloligands: Easy Access to Ir^I/Pd⁰ and Ir^I/Pd⁰/Ir^I Cores