The first direct observation of N–O bond cleavage in the oxidative addition of an oxime to a metal centre. Synthesis and crystal structure of the methyleneamide complex trans-[Re(OH)(NCMe2)(Ph2PCH2CH2PPh2)2][HSO4]

Ferreira, Cristina M. P.; Silva, M. Fátima C. Guedes da; Kukushkin, Vadim Yu.; Silva, João J. R. Fraústo da; Pombeiro, Armando J. L.

doi:10.1039/a707213i

Cited by 46 publications

(28 citation statements)

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“…(1) reaction of R 1 R 2 N À X (as an electrophile) with the metal catalyst (M 1 ) would introduce the amine group to the metal center to form R 1 R 2 N-M 1 -X; [34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] (2) transmetalation of RM 2 (M 2 = B(OH) 2 ) with R 1 R 2 N-M 1 -X to furnish R 1 R 2 N-M 1 R; and (3) final reductive elimination to form the CÀN bond.…”

Section: Dedicated To Professor Xiyan Lu On the Occasion Of His 80th mentioning

confidence: 99%

“…[15,17,21,22] However, electrophilic amination of organometallic reagents by R 1 R 2 N + synthons, [23][24][25][26][27][28][29][30][31] though conceptually feasible, has received much less attention. [32][33][34][35][36][37] The putative catalytic cycle of this transformation is illustrated in Scheme 1:(1) reaction of R 1 R 2 N À X (as an electrophile) with the metal catalyst (M 1 ) would introduce the amine group to the metal center to form R 1 R 2 N-M 1 -X; [34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] (2) transmetalation of RM 2 (M 2 = B(OH) 2 ) with R 1 R 2 N-M 1 -X to furnish R 1 R 2 N-M 1 R; and (3) final reductive elimination to form the CÀN bond.The groups of Liebeskind and Johnson have studied this type of CÀN bond formation employing NÀO derivatives. [32][33][34][35][36][37] N-Chloroamides, though attractive because of the ease of preparation [49][50][51] and the high activities of the N À Cl bond, …”

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Aryl Halide Tolerated Electrophilic Amination of Arylboronic Acids with N‐Chloroamides Catalyzed by CuCl at Room Temperature

et al. 2008

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Dedicated to Professor Xiyan Lu on the occasion of his 80th birthdayTransition-metal-catalyzed aryl C sp2 ÀN bond formation has been intensively studied over the past decade because of the importance of the amines and their derivatives in chemistry related fields.[1-9] The Pd-or Cu-catalyzed formation of anilines from electrophilic aryl halides and nucleophilic primary or secondary amines, pioneered by Buchwald and co-workers and Louie and Hartwig, as well as others, [10][11][12][13][14] is a hallmark reaction in this field. In 1998, Chan et al., Evans et al., and Lam et al. independently developed Cu-mediated oxidative amination of nucleophilic arylboronic acids with amines or other nucleophiles, [16][17][18][19][20] and the methods were later improved to include catalytic versions. [15,17,21,22] However, electrophilic amination of organometallic reagents by R 1 R 2 N + synthons, [23][24][25][26][27][28][29][30][31] though conceptually feasible, has received much less attention. [32][33][34][35][36][37] The putative catalytic cycle of this transformation is illustrated in Scheme 1: (1) reaction of R 1 R 2 N À X (as an electrophile) with the metal catalyst (M 1 ) would introduce the amine group to the metal center to form R 1 R 2 N-M 1 -X; [34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] (2) transmetalation of RM 2 (M 2 = B(OH) 2 ) with R 1 R 2 N-M 1 -X to furnish R 1 R 2 N-M 1 R; and (3) final reductive elimination to form the CÀN bond.The groups of Liebeskind and Johnson have studied this type of CÀN bond formation employing NÀO derivatives. [32][33][34][35][36][37] N-Chloroamides, though attractive because of the ease of preparation [49][50][51] and the high activities of the N À Cl bond, [23,50,51] have seldom been utilized in catalytic electrophilic amination reactions. To the best of our knowledge, Göttlich et al. has primarily studied the Cu-mediated reaction of N-chloroamines with alkenes. [38,39,52] Herein, we communicate our results regarding ligandless copper-catalyzed electrophilic amination of arylboronic acids by N-chloroamides under mild conditions.Our initial experiments of N-chloro-N-phenylacetamide [49] (1 a) and phenylboronic acid (2 a) were carried out by using palladium catalysts. In all attempts, biphenyl was formed instead of the desired N-arylation product (3 a).

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Section: Dedicated To Professor Xiyan Lu On the Occasion Of His 80th mentioning

confidence: 99%

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confidence: 99%

Aryl Halide Tolerated Electrophilic Amination of Arylboronic Acids with N‐Chloroamides Catalyzed by CuCl at Room Temperature

et al. 2008

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“…The multiple bond character of the ReN and CN bonds is reflected by the short Re–N (1.789(3) Å) and N–C (1.302(5) Å) distances. The Re–N distance is slightly shorter than those of reported rhenium azavinylidene complexes L n ReNCR 2 , − , but it is slightly longer than those of reported rhenium imido complexes L n ReNR. − The C–N distance is slightly longer than those of reported azavinylidene complexes. − , The C(1)–P distance (1.781(3) Å) is appreciably longer than that of the PC double bond (1.712(2) Å), but it is slightly shorter than that of the  P – C H 2 single bond (1.808 (2) Å) in Ph 2 PCH 2 PPh 2 C(H)C(O)C 6 H 4 - p -Br . The structural data indicate that both resonance structures 8a(A) and 8a(B) contribute to the structure of 8a , with the former being more important (Scheme ).…”

Section: Results and Discussionmentioning

confidence: 77%

“…The azavinylidene complex ReCl 3 (PMePh 2 ) 2 {NC(PMePh 2 )Me} ( 8a ) is interesting as it represents the first example of an azavinylidene complex with a phosphine (PR 3 ) substituent. Reported azavinylidene complexes are mainly confined to those with H, alkyl, and aryl substituents. , A few rhenium azavinylidene complexes have been reported and were generated by alternative routes, , for example, protonation of nitrile complexes, , deprotonation of imido complexes , and insertion of nitriles …”

Section: Results and Discussionmentioning

confidence: 99%

Azavinylidene Complexes from Coupling Reactions of Organonitriles with Phosphines

et al. 2021

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The reactions of the rhenium(III)-phosphine complex ReCl 3 (PMePh 2 ) 3 with organonitriles (NCR) were studied and found to give novel addition as well as simple substitution products. Refluxing ReCl 3 (PMePh 2 ) 3 in acetonitrile (MeCN) yielded a mixture of the organonitrile rhenium complex ReCl 3 (PMePh 2 ) 2 (NCMe) and the rhenium phosphonium-substituted azavinylidene complex ReCl 3 (PMePh 2 ) 2 {NC(PMePh 2 )-Me}. Similarly, reactions of ReCl 3 (PMePh 2 ) 3 with arylnitriles p-R-C 6 H 4 CN (R = H, Me, and Br) gave the corresponding azavinylidene complexes ReCl 3 (PMePh 2 ) 2 {N C(PMePh 2 )(p-C 6 H 4 R)}. The nitrile complex ReCl 3 (PPh 3 ) 2 (NCPh) is unreactive toward external PPh 3 , but it reacts with excess PMe 3 to produce the azavinylidene complex ReCl 3 (PMe 3 ) 2 {NC(PMe 3 )Ph}. Computational studies reveal the effect of ligand and substituent of organonitriles on the thermodynamics and kinetics for the reactions of ReCl 3 (PR 3 ) 2 (NCR′) with PR 3. Both the experimental and computational results indicate that nucleophilic addition of phosphines to coordinated nitriles is more favorable for nitriles with an electron-withdrawing group and for phosphines which are more electron-donating.

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“…Our group has been involved in the reaction of oximes [24, 25, 26, 27, 28, 29, 30, 31, 32] with metal bound nitriles. Ni(II)-ketoxime mediated transformations of nitriles or/and phthalonitriles were achieved, affording various nickel-ligated species including (i) symmetrical imidoylamidines (1,3,5-triazapentadienes) [24], (ii) phthalocyanines [25] and (iii) unsymmetrical imidoylamidines with imino-isoindolinone moieties [26].…”

Section: Introductionmentioning

confidence: 99%

Distinctive coordination behavior of a pyrazole imine-oxime compound towards Co(II) and Ni(II)

Gupta

Silva

Pombeiro

2019

Heliyon

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The polytopic Schiff base 5-methyl-1H-pyrazole-3-carboxylic acid 2-(hydroxyimino-1-methyl-propylidene)-hydrazide (H 2 L)was synthesized by the condensation of 5-methyl pyrazole-3-carbohydrazide and 3-(hydroxyimino)butan-2-one and its coordination ability was tested against cobalt (II) and nickel (II) nitrates. The ligand exhibited two different binding modes to form a unique binuclear triply bridged Co(III) cationic complex [Co 2 (1κ N 2 :2κ N 2 -L) (1κ N 3 :2κ O 1 -HL) 2 ](NO 3 ) 2 ( 1 ). With the Ni(II) precursor, H 2 L was hydrolyzed to N′,N˝-butane-2,3-diylidenebis (5-methyl-1 H -pyrazole-3-carbohydrazide) (H 2 L 1 ) which bound the metal cation in a tetradentate N 3 O 1 fashion leading to the neutral square planar complex [Ni(κ N 3 O 1 -L 1 )]·MeOH ( 2 ·MeOH). Complexes 1 and 2 were characterized by IR, NMR, UV-Vis and single crystal X-ray crystallography. The probable mechanism for the Ni(II) mediated transformation of H 2 L into H 2 L 1 has been investigated by ESI-MS.

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The first direct observation of N–O bond cleavage in the oxidative addition of an oxime to a metal centre. Synthesis and crystal structure of the methyleneamide complex trans-[Re(OH)(NCMe2)(Ph2PCH2CH2PPh2)2][HSO4]

Cited by 46 publications

References 7 publications

Aryl Halide Tolerated Electrophilic Amination of Arylboronic Acids with N‐Chloroamides Catalyzed by CuCl at Room Temperature

Aryl Halide Tolerated Electrophilic Amination of Arylboronic Acids with N‐Chloroamides Catalyzed by CuCl at Room Temperature

Azavinylidene Complexes from Coupling Reactions of Organonitriles with Phosphines

Distinctive coordination behavior of a pyrazole imine-oxime compound towards Co(II) and Ni(II)

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