O,N-Heterocyclic germylenes as efficient catalysts for hydroboration and cyanosilylation of benzaldehyde

Arsenyeva, Kseniya V.; Pashanova, Kira I.; Trofimova, O. Yu.; Ershova, Irina V.; Chegerev, M. G.; Старикова, А. А.; Cherkasov, Anton V.; Syroeshkin, Mikhail A.; Kozmenkova, Anna Ya.; Piskunov, A. V.

doi:10.1039/d1nj01644j

Cited by 27 publications

(19 citation statements)

References 76 publications

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“…Density functional theory (DFT) calculations were performed using the Gaussian 09 program package [75] at the B3LYP/ Def2TZVP level. The applied approximation was recently shown [76,77] to accurately reproduce the geometry, electronic, and energy characteristics of metal complexes with redox-active ligands. The stationary points on the potential energy surfaces were located by full geometry optimization with the calculation of the force constant matrix and checking for the stabilities of the DFT wave function.…”

Section: Dft Calculationsmentioning

confidence: 99%

Square-Planar Heteroleptic Complexes of α-Diimine-NiII-Catecholate Type: Intramolecular Ligand-to-Ligand Charge Transfer

et al. 2021

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Two heteroleptic NiII complexes combined the redox-active catecholate and 2,2′- bipyridine ligand platforms were synthesized to observe a photoinduced intramolecular ligand-to-ligand charge transfer (LL’CT, HOMOcatecholate → LUMOα-diimine). A molecular design of compound [NiII(3,6-Cat)(bipy)]∙CH3CN (1) on the base of bulky 3,6-di-tert-butyl-o-benzoquinone (3,6-DTBQ) was an annelation of the ligand with an electron donor glycol fragment, producing derivative [NiII(3,6-Catgly)(bipy)]∙CH2Cl2 (2), in order to influence the energy of LL’CT transition. A substantial longwave shift of the absorption peak was observed in the UV-Vis-NIR spectra of 2 compared with those in 1. In addition, the studied NiII derivatives demonstrated a pronounced negative solvatochromism, which was established using a broad set of solvents. The molecular geometry of both compounds can be ascribed as an insignificantly distorted square-planar type, and the π–π intermolecular stacking of the neighboring α-diimines is realized in a crystal packing. There is a lamellar crystal structure for complex 1, whereas the perpendicular T-motifs with the inter-stacks attractive π–π interactions form the packing of complex 2. The redox-active nature of ligand systems was clearly shown through the electrochemical study: a quasi-reversible one-electron reduction of 2,2′-bipyridine and two reversible successive one-electron oxidative conversations (“catecholate dianion—o-benzosemiquinonato radical anion—neutral o-benzoquinone”) were detected.

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Section: Dft Calculationsmentioning

confidence: 99%

Square-Planar Heteroleptic Complexes of α-Diimine-NiII-Catecholate Type: Intramolecular Ligand-to-Ligand Charge Transfer

et al. 2021

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“…[4][5] However, heavier congeners, germylenes and stannylenes, were shown to be competent in catalysis through a diversity of mechanisms. [6][7][8][9][10][11][12][13][14][15][16] The first example is the hydridogermylene [Ar*(iPr 3 Si)NGeH] (Ar* = 2,4,6-iPr{C(H)Ph 2 } 2 C 6 H 2 ) that catalyzes the hydroboration of carbonyl compounds via the GeÀ H and BÀ H σ-bond metathesis reactions. [17] The second example is the phosphine-tetrylene complexes [Ar iPr EC(H)(Ph)PPh 2 ] (E = Ge, Sn; Ar iPr = 2,6-(2,4,6-iPr 3 C 6 H 2 ) 2 C 6 H 3 ), which mediates the catalytic hydroboration of aldehyde via two mechanisms: the activation of aldehyde by forming adduct with the phosphine donor and tetrylene acceptor, as well as the activation of pinacolborane (HBpin) at the tetrylene center.…”

Section: Introductionmentioning

confidence: 99%

Amidinato Isopropylmethylamidosilylene‐Catalyzed Hydroboration of Carbonyl Compounds

et al. 2022

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This study describes the use of an amidinato isopropylmethylamidosilylene [LSiN(Me)iPr] (1, L=PhC(NtBu)2) to catalyze hydroboration of carbonyl compounds. Compound 1 (loading: 5–10 mol%) was shown to be an efficient catalyst for the chemoselective hydroboration of aldehydes (average yield=97 %, average TOF=8.8 h−1) and ketones (average yield=97 %, average TOF=1.7 h−1) with pinacolborane (HBpin) in C6D6 at 90 °C to form borate esters. Mechanistic studies show that the Si lone pair electrons on 1 and the B vacant p orbital of HBpin activates the C=O double bond of aldehydes and ketones, the intermediates of which undergoes hydroboration to yield borate esters and regenerate compound 1.

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“…Hence, the development of efficient metal catalysts for this conversion has attracted considerable attention. [ 10 ]…”

Section: Introductionmentioning

confidence: 99%

“…Hence, the development of efficient metal catalysts for this conversion has attracted considerable attention. [10] Previously, we have studied the complexes of group 14 elements [11a] with o-amidophenolate ligands, including low-valent ones [11] in the course of their versatile reactivity: oxidative addition, ligand oxidation, acid-base properties, reducing the metallocenter, and the electron density distribution. Here, we describe the chemical behavior of a novel O,N-heterocyclic tin(II) derivative ( 1 ,imino) ethyl)phenyl)amino)phenol ( R APH 2 ) has been synthesized through a multistep process (Scheme 2) comprising arylation of 2-aminoacetophenone by 3,5-di-tertbutylcatechol and subsequent condensation of the resulting product with 2-picolylamine.…”

Section: Introductionmentioning

confidence: 99%

Stable heterocyclic stannylene: The metal, ligand‐centered reactivity, and effective catalytic hydroboration of aldehydes

Arsenyeva

Klimashevskaya

Pashanova

et al. 2022

Applied Organom Chemis

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A stable O,N‐heterocyclic stannylene 1 bearing novel tetradentate 2,4‐di‐tert‐butyl‐6‐((2‐(1‐((pyridin‐2‐ylmethyl)imino)ethyl)phenyl)amino)phenolate ligand (RAPH2) was synthesized and characterized. Complex 1 is monomeric in crystal and solution due to two additional intramolecular N → Sn donor–acceptor interactions. The diverse reactivity of compound 1 towards various iron carbonyl compounds was studied. Oxidative addition of [Fe2(μ‐S2)(CO)6]2 to the tin center of 1 resulted in a new six‐coordinate Sn(IV) compound 2 containing two Sn–S bonds. The reaction of 1 with Fe2(CO)9 led to the formation of a stable tin(II) adduct 3 – RAPSn‐Fe(CO)4. The interaction between 1 and [(η5‐C5H5)Fe(CO)2]2 resulted in a transformation of the ligand skeleton. During this reaction, the tin center is oxidized to the tetravalent state, and the donor ═N–CH2–Py group is converted into an anionic one with the loss of the methylene hydrogen atom. The molecular structures of all obtained compounds were determined by single‐crystal X‐ray diffraction. The novel stannylene 1 demonstrates striking activity in benzaldehydes' hydroboration reactions down to 0.02 mole percent of the catalyst loading under mild conditions.

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O,N-Heterocyclic germylenes as efficient catalysts for hydroboration and cyanosilylation of benzaldehyde

Abstract: New monomeric O,N-heterocyclic germylene AdAPGe (1) based on 4,6-di-tert-butyl-N-adamantyl-o-aminophenol is synthesized and structurally characterized. Germylene 1 in the crystal demonstrates weak Ge···Ge interactions between adjacent molecules. The redox activity of...

Cited by 27 publications

References 76 publications

Square-Planar Heteroleptic Complexes of α-Diimine-NiII-Catecholate Type: Intramolecular Ligand-to-Ligand Charge Transfer

Square-Planar Heteroleptic Complexes of α-Diimine-NiII-Catecholate Type: Intramolecular Ligand-to-Ligand Charge Transfer

Amidinato Isopropylmethylamidosilylene‐Catalyzed Hydroboration of Carbonyl Compounds

Stable heterocyclic stannylene: The metal, ligand‐centered reactivity, and effective catalytic hydroboration of aldehydes

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