Coordination Behavior of the (Diphenylphosphanyl)[α‐(2‐pyridyl)benzyl]amide Anion toward Lithium and Zinc Cations

Olbert, Dirk; Görls, Helmar; Conrad, Delf; Westerhausen, Matthias

doi:10.1002/ejic.201000039

Cited by 13 publications

(8 citation statements)

References 31 publications

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“…The transformation of green to yellow ( 2 ) is monitored spectrophotometrically in deaerated tetrahydrofuran (THF) at 313 K (Figure ). 1 H NMR of the in situ generated green solution in benzene- d 6 fails to display the characteristic resonance of C α –H around 3–5.5 ppm (Figure S5f), possibly implying involvement of the dianionic intermediate ( DA , Figure ) in the conversion sequence. , DA 2 (Figure ) was selectively chosen to follow because phenyl substitution at the methine carbon of HL2 has extended additional stability to the system via conjugation of C α – ( DA 2 ) into the phenyl ring along with the pyridyl moiety.…”

Section: Results and Discussionmentioning

confidence: 99%

“…Therefore, a common dianionic intermediate ( DA ), generated via activation of the acidic methylene group of PA upon coordination to electrophilic {Ru(H/Cl)(CO)(PPh 3 ) 2 } or {Ru(pap) 2 }, is considered to correlate the reactivity patterns. , The reactive C α center of DA 1 (no longer “spectator”) reacts with the molecular oxygen in an intermolecular fashion to yield 1 . However, the presence of an electrophilic substituent at DA 4 facilitates the intramolecular reaction between the carbonyl center and reactive C α , leading to the formation of a cyclized product in 4 .…”

Section: Results and Discussionmentioning

confidence: 99%

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Diverse Functionalization of Ruthenium-Chelated 2-Picolylamines: Oxygenation, Dehydrogenation, Cyclization, and N-Dealkylation

et al. 2020

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Chemical noninnocence" of metal-coordinated 2-picolylamine (PA) derivatives has been introduced upon its reaction with the metal precursor [Ru II (Cl)-(H)(CO)(PPh 3 ) 3 ] under basic conditions. This in effect leads to the facile formation of metalated amide, imine, ring-cyclized pyrrole, and an N-dealkylated congener based on the fine-tuning of an amine nitrogen (N amine ) and a methylene center (C α ) at the PA backbone. It develops oxygenated L1′ in 1 and cyclized L4′ in 4 upon switching of the N amine substituent of PA from aryl to an electrophilic pent-3-en-2-one moiety. On the other hand, imposing the substituent at the C α position of PA modifies its reactivity profile, leading to a dehydrogenation (2/3) or N-dealkylation (6) process. The divergent reactivity profile of metalated PA is considered to proceed through a common dianionic intermediate. Further, a competitive scenario of C−H bond functionalization of coordinated PA versus the ligand-exchange process has been exemplified in the presence of external electrophile such as benzyl bromide or methylene iodide. Authentication of the product formation as well as elucidation of the reaction pathway has been addressed by their crystal structures and spectroscopic features in conjunction with the transition-state (TS) theory.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Diverse Functionalization of Ruthenium-Chelated 2-Picolylamines: Oxygenation, Dehydrogenation, Cyclization, and N-Dealkylation

et al. 2020

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“…DEI-mass spectra were obtained on a Finnigan MAT SSQ 710 system (2,4-dimethoxybenzyl alcohol as matrix), IR measurements were carried out on a Perkin-Elmer System 2000 FT-IR. Starting [(thf)-Fe{N(SiMe 3 ) 2 } 2 Cl], [36,41] Py-CH 2 -N(H)-PPh 2 (1), [28] and Py-C(Ph)-H-N(H)-PPh 2 [42] were prepared according to literature procedures. (4) …”

Section: Methodsmentioning

confidence: 99%

Influence of N‐Substitution on the Oxidation of 2‐Pyridylmethylamines with Bis(trimethylsilyl)amides of Iron(III) – Synthesis of Heteroleptic Iron(II) 2‐Pyridylmethylamides

et al. 2011

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The reaction of (thf)Fe[N(SiMe3)2]2Cl with (2‐pyridylmethyl)(diphenylphosphanyl)amine (1) in hot tetrahydrofuran (THF) yields dinuclear [(ClFe)2{μ‐N(SiMe3)2}{Ph2P(NCH2Py)2}] (2) and [ClFe{Ph2P(O)‐NCH2Py}]2 (3) with the oxygen atom stemming from THF degradation. The formation of 2 requires a P–N bond cleavage and reformation leading to the tetradendate diphenyl‐bis(2‐pyridylmethylamido)phosphonium ion. If this reaction of (thf)Fe[N(SiMe3)2]2Cl with 1 is performed at room temperature, no P–N bond cleavage is observed. Instead of that, ether degradation occurs yielding [Fe4(μ4‐O)(μ2‐Cl)2(Ph2P‐NCH2Py)4] (4) with a central oxygen‐centered iron tetrahedron as well as complex 3. Recrystallization of 3 from dichloromethane leads to addition of HCl and to the formation of [FeCl2·{Ph2P(O)‐N(H)‐CH2Py}] (5). The phosphonium ion of 2 is isoelectronic to the corresponding diphenyl‐bis(2‐pyridylmethylamino)silane (6). Lithiation of 6 followed by a metathetical reaction with (thf)2FeCl2 yields the trinuclear complex [Fe3Cl2{Ph2Si(NCH2Py)2}2] (7) with antiferromagnetic interactions.

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“…All preparations were performed under aerobic conditions using chemicals and solvents as received, unless otherwise stated. mpkoH [41] and ppkoH [42] were prepared as described. Selected crystal data and refinement parameters are listed in Table 1.…”

Section: Synthesismentioning

confidence: 99%

New mixed-valence MnII4MnIV clusters from an unusual ligand transformation

2017

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The syntheses, crystal structures and magnetic properties are reported of two new and unusual mixed-valence Mn clusters [Mn II 4 Mn IV O(mpko) 5 (MeO-hmp)(mpko-hmp)(H 2 O)](ClO 4) 3 (1) and [Mn II 4 Mn IV O(ppko) 5 (MeO-hmp)(ppko-hmp)(H 2 O)](ClO 4) 3 (2). They were obtained from the reaction of mpkoH or ppkoH and hmpH with Mn(ClO 4) 2 in the presence of NaOMe, where mpkoH is methyl(pyridin-2-yl)ketone oxime, ppkoH is phenyl(pyridin-2-yl)ketone oxime, and hmpH is 2-(hydroxymethyl)pyridine. Complex 1 possesses a distorted Mn II 4 cubane core attached to an external Mn IV by the O 2ion. The peripheral ligation includes two unprecedented hemiacetal ligands formed in situ from the reaction of hmpH with MeOH or mpkoH/ppkoH. Solid-state dc and ac magnetic susceptibility measurements established that both 1 and 2 possess an S = 7 / 2 ground state, which was confirmed by ac in-phase susceptibility data. Simulations of the χ M T vs T data established the presence of dominant antiferromagnetic exchange interactions, rationalizing the observed ground state.

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Coordination Behavior of the (Diphenylphosphanyl)[α‐(2‐pyridyl)benzyl]amide Anion toward Lithium and Zinc Cations

Cited by 13 publications

References 31 publications

Diverse Functionalization of Ruthenium-Chelated 2-Picolylamines: Oxygenation, Dehydrogenation, Cyclization, and N-Dealkylation

Diverse Functionalization of Ruthenium-Chelated 2-Picolylamines: Oxygenation, Dehydrogenation, Cyclization, and N-Dealkylation

Influence of N‐Substitution on the Oxidation of 2‐Pyridylmethylamines with Bis(trimethylsilyl)amides of Iron(III) – Synthesis of Heteroleptic Iron(II) 2‐Pyridylmethylamides

New mixed-valence MnII4MnIV clusters from an unusual ligand transformation

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