π(Arene) versus donor ligand complexation in the formation of the heterobimetallic lithium–potassium dianion of (S)-N-(α-methylbenzyl)allylamine

Andrews, Philip C.; Calleja, S.; Maguire, Melissa

doi:10.1016/j.jorganchem.2005.07.006

Cited by 8 publications

(5 citation statements)

References 49 publications

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“…However, spectroscopic evidence for cation-π-interactions in solution has been extremely limited 32 . The study aimed of determining a structure and stability of the complex formed in aged solution is in progress and will be published elsewhere.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Functional Derivatives of 7,8-Dicarba-nido-undecaborate Anion by Ring-Opening of Its Cyclic Oxonium Derivatives

Stogniy

Abramova

Lobanova

et al. 2007

Collect. Czech. Chem. Commun.

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A new approach to synthesis of functional derivatives of 7,8-dicarba-nido-undecaborate anion based on ring-opening of its cyclic oxonium derivatives [10-(CH 2 ) 4 O-7,8-C 2 B 9 H 11 ] and [10-O(CH 2 CH 2 ) 2 O-7,8-C 2 B 9 H 11 ] with various nucleophiles was developed. Both cyclic oxonium derivatives can be obtained as single isomers by reaction of the parent anion [7,8-C 2 B 9 H 12 ] -with mercury(II) chloride in the corresponding solvents. Mechanism of formation of the cyclic oxonium derivatives of 7,8-dicarba-nido-undecaborate anion was proposed. A series of 7,8-dicarba-nido-undecaborate derivatives with terminal carboxylic and azide functions were prepared by the ring-opening reactions of the cyclic oxonium derivatives with substituted phenolate and azide ions, respectively.

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Section: Resultsmentioning

confidence: 99%

Synthesis of Functional Derivatives of 7,8-Dicarba-nido-undecaborate Anion by Ring-Opening of Its Cyclic Oxonium Derivatives

Stogniy

Abramova

Lobanova

et al. 2007

Collect. Czech. Chem. Commun.

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“…Complementary investigations examining the ability of host systems incorporating alkali metals to coordinate neutral arene molecules have similarly been completed. [4] Cation-p interactions also play a critical role in determining the course of many reactions involving s-block metal reagents, [19][20][21][22] and their presence has been exploited in various materials chemistry applications, [23][24][25][26][27] such as the preparation of ultrathin nanotubes. [28] Abstract: Addition of ferrocene to so- 3 -network through doubly h 3 -coordinated bisA C H T U N G T R E N N U N G (benzene)chromium molecules.…”

Section: Introductionmentioning

confidence: 99%

Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me₃Si)₂NM}₂⋅(Cp₂Fe)]_∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)

Morris

Noll

Honeyman

et al. 2007

Chemistry A European J

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Addition of ferrocene to solutions of alkali metal hexamethyldisilazides M(HMDS) in arenes (in which M=Na, K, Rb, Cs) allows the subsequent crystallization of the homologous series of compounds [{(Me(3)Si)(2)NM}(2) (Cp(2)Fe)](infinity) (1-4). Similar reactions using LiHMDS led to the recrystallization of the starting materials. The crystal structures of 1-4 reveal the formation of one-dimensional chains composed of dimeric [{M(HMDS)}(2)] aggregates, which are bridged through neutral ferrocene molecules by eta(5)-cation-pi interactions. In addition, compounds 3 and 4 also contain interchain agostic M--C interactions, producing two-dimensional 4(4)-nets. Whereas 1 and 2 were prepared from toluene, the syntheses of 3 and 4 required the use of tert-butylbenzene as the reaction media. The attempted crystallization of 3 and 4 from toluene resulted in formation of the mixed toluene/ferrocene solvated complexes [{(Me(3)Si)(2)NM)(2)}(2) (Cp(2)Fe)(x)(Tol)(y)](infinity) (in which M=Rb, x=0.6, y=0.8, 5; M=Cs, x=0.5, y=1, 6). The extended solid-state structures of 5 and 6 are closely related to the 4(4)-sheets 3 and 4, but are now assembled from a combination of cation-pi, agostic, and pi-pi interactions. The charge-separated complex [K{(C(6)H(6))(2)Cr}(1.5)(Mes)][Mg(HMDS)(3)] (15) was also structurally characterized and found to adopt an anionic two-dimensional 6(3)-network through doubly eta(3)-coordinated bis(benzene)chromium molecules. DFT calculations at the B3 LYP/6-31G* level of theory indicate that the binding energies of both ferrocene and toluene to the M(HMDS) dimers increases in the sequence Li

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“…This suggests that the formation of [(PhCCH 2 )(CHC(CH 2 CH 2 CH 3 )CH 3 )NNa] is not dependent specifically on the presence of THF. Arenes can act as “nonclassical” Lewis donors with alkali metals mimicking the effect of more typical solvents . The d 8 -THF sample was monitored over time, and by 3 days there is no longer any of the initially formed 1-azaallyl species left.…”

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confidence: 99%

The Strange Case of Sodium (S)-N-α-(Methylbenzyl)allylamide: Anion Rearrangement, Decomposition, and a Peculiar Propyl Addition

2016

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An unexpected aza-enolate propyl addition complex, [(PhCCH2)(CHC(CH2CH2CH3)CH3)NNa·THF]∞ (1), was isolated when (S)-N-α-(methylbenzyl)allylamine reacted in hexane with nBuNa in the presence of THF. Analytical studies revealed a decomposition of the sodium 1-azaallylamide to a sodium enamide and propene, identified by solution studies and a GC-headspace study, respectively. Propene then adds to the carbanion tautomer of the sodium 1-azaallylamide followed by anionic rearrangements to later form the aza-enolate propyl addition complex.

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π(Arene) versus donor ligand complexation in the formation of the heterobimetallic lithium–potassium dianion of (S)-N-(α-methylbenzyl)allylamine

Cited by 8 publications

References 49 publications

Synthesis of Functional Derivatives of 7,8-Dicarba-nido-undecaborate Anion by Ring-Opening of Its Cyclic Oxonium Derivatives

Synthesis of Functional Derivatives of 7,8-Dicarba-nido-undecaborate Anion by Ring-Opening of Its Cyclic Oxonium Derivatives

Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me₃Si)₂NM}₂⋅(Cp₂Fe)]_∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)

The Strange Case of Sodium (S)-N-α-(Methylbenzyl)allylamide: Anion Rearrangement, Decomposition, and a Peculiar Propyl Addition

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π(Arene) versus donor ligand complexation in the formation of the heterobimetallic lithium–potassium dianion of (S)-N-(α-methylbenzyl)allylamine

Cited by 8 publications

References 49 publications

Synthesis of Functional Derivatives of 7,8-Dicarba-nido-undecaborate Anion by Ring-Opening of Its Cyclic Oxonium Derivatives

Synthesis of Functional Derivatives of 7,8-Dicarba-nido-undecaborate Anion by Ring-Opening of Its Cyclic Oxonium Derivatives

Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me3Si)2NM}2⋅(Cp2Fe)]∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)

The Strange Case of Sodium (S)-N-α-(Methylbenzyl)allylamide: Anion Rearrangement, Decomposition, and a Peculiar Propyl Addition

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Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me₃Si)₂NM}₂⋅(Cp₂Fe)]_∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)