REACTIVITY OF NITROSODICYANOMETHANIDE TOWARDS Ni(II)

Hvastijová, Mária; Kožı́šek, Jozef; Kohout, Jiřĺ; Jäger, Lothar

doi:10.1080/00958979508022561

Cited by 19 publications

(11 citation statements)

References 12 publications

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“…Several bonding motifs can be expected because apart from oxygen and the central nitrogen, end-on nitrile groups can also be discussed as potential donor atoms. [8] . In this context the [᭛] Part XII: Ref.…”

Section: } 2 ]mentioning

confidence: 95%

“…In both species oxygen and the middle tal ions in complexes with this ligand (in a uni-and esnitrogen atoms should be comparable from the electronic pecially in a bidentate function) we prepared compounds of point of view [3] . According to the soft-soft and hard-hard copper(I) and silver( [5] , Pt II [6] ) whilst more hard 3d-metal ions (Ni II [7] , Cu II [8] , Co III [8] , Fe III [5] ) coordinate via the oxygen atom. In contrast to this finding the ion [N{C(CN) 2 …”

Section: } 2 ]mentioning

confidence: 99%

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On the Ambident Behaviour of Dicyanmethanidonitrite; Syntheses and Characterization of Complexes of the Type [M{N(O)C(CN)2}(PPh3)n] (M = CuI, AgI;n = 2, 3)

Jäger

Tretner

Hartung

et al. 1998

Eur. J. Inorg. Chem.

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Section: } 2 ]mentioning

confidence: 95%

Section: } 2 ]mentioning

confidence: 99%

On the Ambident Behaviour of Dicyanmethanidonitrite; Syntheses and Characterization of Complexes of the Type [M{N(O)C(CN)2}(PPh3)n] (M = CuI, AgI;n = 2, 3)

Jäger

Tretner

Hartung

et al. 1998

Eur. J. Inorg. Chem.

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“…This experimental evidence supports the reports in the literature that the addition of alcohols to the dcnm anion only proceeds in the presence of a transition metal cation. 31,[33][34][35][36][37][38][39] Optimized geometries of the methanol addition products are shown in Figure 9, and the reaction enthalpies for both steps of methanol addition are presented in Table 4. In the case of the first methanol addition the reaction enthalpies are less exothermic by about 30 kJ mol -1 compared to those of water.…”

Section: Table 2: Reaction Enthalpies (In Kj Mol -1 ) Of Water Additimentioning

confidence: 99%

“…[20][21][22][23][24][25][26] The dicyanonitrosomethanide anion (dcnm, [C(CN) 2 (NO)] -) [27][28][29] has been demonstrated to have an even greater propensity to undergo this reaction. For the dcnm anion, the reaction has been shown to occur under three distinct sets of conditions: (1) in the presence of a transition metal, which may promote the addition of water, an alcohol or an amine, [30][31][32][33][34][35][36][37][38][39][40] (2) in the presence of an acid, which may promote the addition of an amine, [41][42][43] or (3) by heating an aqueous reaction solution containing the dcnm anion with a nonmetallic countercation to reflux, which has been shown to result in the addition of water, giving the carbamoylcyanonitrosomethanide anion (ccnm, [C(CN)(CONH 2 )(NO)] -), as shown in Figure 1. 44 Despite numerous literature reports, certain aspects of this reaction are yet to be adequately understood, namely why the addition of an amine may occur to both of the nitrile groups of the dcnm anion while water or alcohols have been observed to react only with one nitrile group.…”

Section: Introductionmentioning

confidence: 99%

Theoretical and Experimental Insights into the Mechanism of the Nucleophilic Addition of Water and Methanol to Dicyanonitrosomethanide

et al. 2010

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In this work the nucleophilic addition of water and methanol to the dicyanonitrosomethanide anion (dcnm, [C(CN)(2)(NO)](-)) in the absence of the usual transition metal promoters was investigated. Experimentally it was shown that a quantitative conversion of the dcnm anion to carbamoylcyanonitrosomethanide (ccnm, [C(CN)(CONH(2))(NO)](-)) by the addition of 1 equiv of water to a nitrile group is complete in 48 h at 100 °C, or in 1.5 h at 150 °C when the reaction is conducted in a microwave reactor. Attempts to add a second equivalent of water to the anion failed with thermal degradation of the anion occurring at 200 °C. Ab initio calculations show that the reaction proceeds via three distinct transition states: (1) the transfer of a proton from a water molecule to the nitrile group, (2) the subsequent attack of the generated hydroxide anion on the carbon atom of the nitrile group, and (3) a rapid proton transfer to form a carbamoyl group. The attacking water molecule is shown to be a stronger proton donor when modeled as part of a hydrogen-bonded three water molecule chain, leading to a significant reduction in the reaction barrier. Only the anti-ccnm anion is formed in the reaction. There is a high-energy barrier to the formation of the syn isomer by the rotation of the nitroso group. While the syn isomer of ccnm is shown to be the more thermodynamically stable conformation, examination of the HOMO-1 molecular orbital that arises during the second transition state of the reaction indicates the addition of the hydroxide anion to the carbon atom is forbidden due to orbital symmetry, with a similar effect responsible for the failure of a second equivalent of water to add to the ccnm anion. Under analogous reaction conditions the addition of 1 equiv of methanol to dcnm to form cyano(imino(methoxy)methyl)nitrosomethanide (cmnm, [C(CN)(C(OMe)NH)(NO)](-)) failed, although ab initio calculations initially indicated the reaction should proceed more readily than the addition of water. When the energy required to break the hydrogen-bonded cyclic hexamers in methanol is taken into consideration, the energy barrier to the first transition step is greatly increased. The addition of a second equivalent of methanol to cmnm is unlikely to occur even in the presence of a transition metal as the resultant anion would be marginally thermodynamically unstable.

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“…On the other hand, according to [16], the anionic chelate ligand cenm is formed by nucleophilic addition of the ethanol oxygen to the cyano carbon of the nitroso nitrogen coordinated dcnm anion. This carbon possesses some positive charge which activates it for electrophilic function.…”

Section: Introductionmentioning

confidence: 99%

Low-dimensional compounds containing cyanido groups. Part XXXI. First simultaneous nucleophilic addition of water and ethanol to dicyanonitrosomethanide anions in the presence of Co(II)

Vitushkina

Teslenko

Váhovská

et al. 2017

Inorganica Chimica Acta

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REACTIVITY OF NITROSODICYANOMETHANIDE TOWARDS Ni(II)

Cited by 19 publications

References 12 publications

On the Ambident Behaviour of Dicyanmethanidonitrite; Syntheses and Characterization of Complexes of the Type [M{N(O)C(CN)2}(PPh3)n] (M = CuI, AgI;n = 2, 3)

On the Ambident Behaviour of Dicyanmethanidonitrite; Syntheses and Characterization of Complexes of the Type [M{N(O)C(CN)2}(PPh3)n] (M = CuI, AgI;n = 2, 3)

Theoretical and Experimental Insights into the Mechanism of the Nucleophilic Addition of Water and Methanol to Dicyanonitrosomethanide

Low-dimensional compounds containing cyanido groups. Part XXXI. First simultaneous nucleophilic addition of water and ethanol to dicyanonitrosomethanide anions in the presence of Co(II)

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