Deprotonation and reductive addition reactions of hypervalent aluminium dihydride compounds containing substituted pyrrolyl ligands with phenols, ketones, and aldehydes

I. Chun Chen, Shi Mau Ho, Ya Chi Chen, Che Yu Lin, Ching Han Hu, Cheng Yi Tu, Amitabha Datta, Jui Hsien Huang, Chia Her Lin

Research output: Contribution to journalArticle

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Abstract

The reactivities of [C4H2N(CH2NMe 2)2]AlH2 (1) with primary and secondary amines, phenols, ketones, and phenyl isothiocyanate were examined. Reactions of 1 with one or two equivalents of 2,6-dichloroaniline in methylene chloride generated [C4H2N(CH2NMe2)2] AlH(NHC6H3-2,6-Cl2) (2) and [C 4H2N(CH2NMe2)2] Al(NHC6H3-2,6-Cl2)2 (3), respectively, following hydrogen elimination. Similarly, the reactions of 1 with one or two equivalents of carbazole afforded [C4H 2N(CH2NMe2)2]AlH(NC 12H8) (4) or [C4H2N(CH 2NMe2)2]Al(NC12H8) 2 (5) by deprotonating the acidic N-H of carbazole. Reacting 1 with one equivalent of 2,6-diisopropylphenol in diethyl ether formed an aluminium phenoxo compound [C4H2N(CH2NMe 2)2]AlH(OC6H3-2,6- iPr2) (6), by deprotonation of phenol as well with the elimination of one equivalent hydrogen. Further reaction of 6 with one equivalent of 2,4,6-trimethylacetophenone in methylene chloride generated [C4H2N(CH2NMe2)2] Al(OC6H3-2,6-iPr2)[OC(CH 2)(C6H2-2,4,6-Me3)] (7) by deprotonating the methyl proton of the acetophenone. Similar deprotonation occurred when 1 reacted with two equivalents of 2,4,6-trimethylacetophenone in methylene chloride to generate [C4H2N(CH 2NMe2)2]Al[OC(CH2)(C 6H2-2,4,6-Me3)]2 (8). Compounds [C4H2N(CH2NMe2)2] Al(OCHPh2)2 (9), and [C4H2N(CH 2NMe2)2]Al(SCHNPh)2 (10) could also be obtained by reacting 1 with two equivalents of benzophenone and phenyl isothiocyanate, respectively through hydroalumination. The 1H NMR spectra of 10 showed broad signals for the CH2N and NMe2 groups, which represent dynamical fluctuations of the molecules in solution state. The estimated energy barrier (ΔGc) from the coalescence temperature for the fluctuation was estimated at 17.1 Kcal mol-1. The solid-state structures of compounds 2, 3, 5, 7, 9, and 10 have been determined.

Original languageEnglish
Pages (from-to)8631-8643
Number of pages13
JournalDalton Transactions
Issue number40
DOIs
Publication statusPublished - 2009 Oct 28

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Aluminum compounds
Deprotonation
Addition reactions
Phenols
Methylene Chloride
Ketones
Aldehydes
Ligands
Hydrogen
Aluminum Compounds
Energy barriers
Propofol
Phenol
Coalescence
Ether
Amines
Protons
Nuclear magnetic resonance
Molecules
Temperature

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

@article{c57d42ff7b04488c90ee67047365c349,
title = "Deprotonation and reductive addition reactions of hypervalent aluminium dihydride compounds containing substituted pyrrolyl ligands with phenols, ketones, and aldehydes",
abstract = "The reactivities of [C4H2N(CH2NMe 2)2]AlH2 (1) with primary and secondary amines, phenols, ketones, and phenyl isothiocyanate were examined. Reactions of 1 with one or two equivalents of 2,6-dichloroaniline in methylene chloride generated [C4H2N(CH2NMe2)2] AlH(NHC6H3-2,6-Cl2) (2) and [C 4H2N(CH2NMe2)2] Al(NHC6H3-2,6-Cl2)2 (3), respectively, following hydrogen elimination. Similarly, the reactions of 1 with one or two equivalents of carbazole afforded [C4H 2N(CH2NMe2)2]AlH(NC 12H8) (4) or [C4H2N(CH 2NMe2)2]Al(NC12H8) 2 (5) by deprotonating the acidic N-H of carbazole. Reacting 1 with one equivalent of 2,6-diisopropylphenol in diethyl ether formed an aluminium phenoxo compound [C4H2N(CH2NMe 2)2]AlH(OC6H3-2,6- iPr2) (6), by deprotonation of phenol as well with the elimination of one equivalent hydrogen. Further reaction of 6 with one equivalent of 2,4,6-trimethylacetophenone in methylene chloride generated [C4H2N(CH2NMe2)2] Al(OC6H3-2,6-iPr2)[OC(CH 2)(C6H2-2,4,6-Me3)] (7) by deprotonating the methyl proton of the acetophenone. Similar deprotonation occurred when 1 reacted with two equivalents of 2,4,6-trimethylacetophenone in methylene chloride to generate [C4H2N(CH 2NMe2)2]Al[OC(CH2)(C 6H2-2,4,6-Me3)]2 (8). Compounds [C4H2N(CH2NMe2)2] Al(OCHPh2)2 (9), and [C4H2N(CH 2NMe2)2]Al(SCHNPh)2 (10) could also be obtained by reacting 1 with two equivalents of benzophenone and phenyl isothiocyanate, respectively through hydroalumination. The 1H NMR spectra of 10 showed broad signals for the CH2N and NMe2 groups, which represent dynamical fluctuations of the molecules in solution state. The estimated energy barrier (ΔGc‡) from the coalescence temperature for the fluctuation was estimated at 17.1 Kcal mol-1. The solid-state structures of compounds 2, 3, 5, 7, 9, and 10 have been determined.",
author = "Chen, {I. Chun} and Ho, {Shi Mau} and Chen, {Ya Chi} and Lin, {Che Yu} and Hu, {Ching Han} and Tu, {Cheng Yi} and Amitabha Datta and Huang, {Jui Hsien} and Lin, {Chia Her}",
year = "2009",
month = "10",
day = "28",
doi = "10.1039/b908164j",
language = "English",
pages = "8631--8643",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "40",

}

Deprotonation and reductive addition reactions of hypervalent aluminium dihydride compounds containing substituted pyrrolyl ligands with phenols, ketones, and aldehydes. / Chen, I. Chun; Ho, Shi Mau; Chen, Ya Chi; Lin, Che Yu; Hu, Ching Han; Tu, Cheng Yi; Datta, Amitabha; Huang, Jui Hsien; Lin, Chia Her.

In: Dalton Transactions, No. 40, 28.10.2009, p. 8631-8643.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Deprotonation and reductive addition reactions of hypervalent aluminium dihydride compounds containing substituted pyrrolyl ligands with phenols, ketones, and aldehydes

AU - Chen, I. Chun

AU - Ho, Shi Mau

AU - Chen, Ya Chi

AU - Lin, Che Yu

AU - Hu, Ching Han

AU - Tu, Cheng Yi

AU - Datta, Amitabha

AU - Huang, Jui Hsien

AU - Lin, Chia Her

PY - 2009/10/28

Y1 - 2009/10/28

N2 - The reactivities of [C4H2N(CH2NMe 2)2]AlH2 (1) with primary and secondary amines, phenols, ketones, and phenyl isothiocyanate were examined. Reactions of 1 with one or two equivalents of 2,6-dichloroaniline in methylene chloride generated [C4H2N(CH2NMe2)2] AlH(NHC6H3-2,6-Cl2) (2) and [C 4H2N(CH2NMe2)2] Al(NHC6H3-2,6-Cl2)2 (3), respectively, following hydrogen elimination. Similarly, the reactions of 1 with one or two equivalents of carbazole afforded [C4H 2N(CH2NMe2)2]AlH(NC 12H8) (4) or [C4H2N(CH 2NMe2)2]Al(NC12H8) 2 (5) by deprotonating the acidic N-H of carbazole. Reacting 1 with one equivalent of 2,6-diisopropylphenol in diethyl ether formed an aluminium phenoxo compound [C4H2N(CH2NMe 2)2]AlH(OC6H3-2,6- iPr2) (6), by deprotonation of phenol as well with the elimination of one equivalent hydrogen. Further reaction of 6 with one equivalent of 2,4,6-trimethylacetophenone in methylene chloride generated [C4H2N(CH2NMe2)2] Al(OC6H3-2,6-iPr2)[OC(CH 2)(C6H2-2,4,6-Me3)] (7) by deprotonating the methyl proton of the acetophenone. Similar deprotonation occurred when 1 reacted with two equivalents of 2,4,6-trimethylacetophenone in methylene chloride to generate [C4H2N(CH 2NMe2)2]Al[OC(CH2)(C 6H2-2,4,6-Me3)]2 (8). Compounds [C4H2N(CH2NMe2)2] Al(OCHPh2)2 (9), and [C4H2N(CH 2NMe2)2]Al(SCHNPh)2 (10) could also be obtained by reacting 1 with two equivalents of benzophenone and phenyl isothiocyanate, respectively through hydroalumination. The 1H NMR spectra of 10 showed broad signals for the CH2N and NMe2 groups, which represent dynamical fluctuations of the molecules in solution state. The estimated energy barrier (ΔGc‡) from the coalescence temperature for the fluctuation was estimated at 17.1 Kcal mol-1. The solid-state structures of compounds 2, 3, 5, 7, 9, and 10 have been determined.

AB - The reactivities of [C4H2N(CH2NMe 2)2]AlH2 (1) with primary and secondary amines, phenols, ketones, and phenyl isothiocyanate were examined. Reactions of 1 with one or two equivalents of 2,6-dichloroaniline in methylene chloride generated [C4H2N(CH2NMe2)2] AlH(NHC6H3-2,6-Cl2) (2) and [C 4H2N(CH2NMe2)2] Al(NHC6H3-2,6-Cl2)2 (3), respectively, following hydrogen elimination. Similarly, the reactions of 1 with one or two equivalents of carbazole afforded [C4H 2N(CH2NMe2)2]AlH(NC 12H8) (4) or [C4H2N(CH 2NMe2)2]Al(NC12H8) 2 (5) by deprotonating the acidic N-H of carbazole. Reacting 1 with one equivalent of 2,6-diisopropylphenol in diethyl ether formed an aluminium phenoxo compound [C4H2N(CH2NMe 2)2]AlH(OC6H3-2,6- iPr2) (6), by deprotonation of phenol as well with the elimination of one equivalent hydrogen. Further reaction of 6 with one equivalent of 2,4,6-trimethylacetophenone in methylene chloride generated [C4H2N(CH2NMe2)2] Al(OC6H3-2,6-iPr2)[OC(CH 2)(C6H2-2,4,6-Me3)] (7) by deprotonating the methyl proton of the acetophenone. Similar deprotonation occurred when 1 reacted with two equivalents of 2,4,6-trimethylacetophenone in methylene chloride to generate [C4H2N(CH 2NMe2)2]Al[OC(CH2)(C 6H2-2,4,6-Me3)]2 (8). Compounds [C4H2N(CH2NMe2)2] Al(OCHPh2)2 (9), and [C4H2N(CH 2NMe2)2]Al(SCHNPh)2 (10) could also be obtained by reacting 1 with two equivalents of benzophenone and phenyl isothiocyanate, respectively through hydroalumination. The 1H NMR spectra of 10 showed broad signals for the CH2N and NMe2 groups, which represent dynamical fluctuations of the molecules in solution state. The estimated energy barrier (ΔGc‡) from the coalescence temperature for the fluctuation was estimated at 17.1 Kcal mol-1. The solid-state structures of compounds 2, 3, 5, 7, 9, and 10 have been determined.

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