Ferromagnetic Coupling Promoted by κ3N:κ2N Bridging System

Igashira‐Kamiyama, Asako; Kajiwara, Takashi; Konno, Takumi; Ito, Tasuku

doi:10.1021/ic0520925

Cited by 23 publications

(21 citation statements)

References 25 publications

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“…Thus, the molecule of I consists of the three planar units adopting the staircase-like structure. The similar molecular conformation has been previously observed in the related compounds (Zhang et al, 2005;Igashira-Kamiyama et al, 2006;Figiel et al, 2010). Nevertheless, it is important to note that the analogous complexes can adopt the planar conformation also (Boča et al, 1996;Kajiwara et al, 2002;Zheng et al, 2007).…”

Section: S1 Commentsupporting

confidence: 88%

“…For a catalytic olefination reaction, see: Shastin et al (2001); Korotchenko et al (2001); Nenajdenko et al (2003Nenajdenko et al ( , 2004aNenajdenko et al ( ,b,c, 2005Nenajdenko et al ( , 2007. For related compounds, see: Boča et al (1996); Kajiwara et al (2002); Zhang et al (2005); Igashira-Kamiyama et al (2006); Zheng et al (2007); Figiel et al (2010). = 103.662 (5) V = 552.1 (3) Å 3 Z = 1 Mo K radiation = 2.45 mm À1 T = 296 K 0.33 Â 0.24 Â 0.06 mm…”

Section: Related Literaturementioning

confidence: 99%

See 1 more Smart Citation

[N-(1-Azanidyl-2,2,2-trichloroethylidene)-2,2,2-trichloroethanimidamide]copper(II)

Shikhaliyev¹,

Maharramov²,

Muzalevskiy³

et al. 2012

Acta Cryst E

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The title compound, [Cu(C4H2Cl6N3)2], was obtained by the reaction of CCl3CN with ammonia in presence of CuCl. The CuII atom is located about an inversion centre. The molecule consists of three planar units (one central square CuN4 and two C2N3 fragments), adopting a staircase-like structure. The six-membered metallocycles have a sofa conformation with the Cu atom out of the plane of the 1,3,5-triazapentadienyl ligands by 0.246 (5) Å. The ipso-C atoms of the CCl3 substituents are slightly out of the 1,3,5-triazapentadienyl planes by 0.149 (6) and −0.106 (6) Å. The CCl3 groups of each 1,3,5-triazapentadienyl ligand are practically in the energetically favourable mutually eclipsed conformation. In the crystal, the molecules are packed in stacks along the a axis. The molecules in the stacks are held together by two additional axial Cu⋯Cl interactions of 3.354 (2) Å. Taking the axial Cu⋯Cl interactions into account, the CuII atom exhibits a distorted [4 + 2]-octahedral coordination environment. The stacks are bound to each other by weak intermolecular attractive Cl⋯Cl [3.505 (2)–3.592 (3) Å] interactions.

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Section: S1 Commentsupporting

confidence: 88%

Section: Related Literaturementioning

confidence: 99%

[N-(1-Azanidyl-2,2,2-trichloroethylidene)-2,2,2-trichloroethanimidamide]copper(II)

Shikhaliyev¹,

Maharramov²,

Muzalevskiy³

et al. 2012

Acta Cryst E

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“…Of further importance, from a structural perspective, when auxiliary L ligands are introduced to the ternary M II -dca-L systems, different coordination architectures, such as mononuclear and dinuclear compounds [49], 1D chains [50][51][52][53][54][55][56][57][58], 2D (4,4) or (6,3) [59][60][61][62][63] sheets, and 3D network topologies [64][65][66][67], could be constructed (Scheme 1). Interestingly, interesting in situ nucleophilic addition reactions were observed between dca and the auxiliary ligands [68][69][70][71][72][73]. On the other hand, weak interactions such as hydrogen bonding andinteractions play an important role for construction of high-dimensional supramolecular systems [74][75][76].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystal Structures, and Magnetic Properties of Ternary M(II)-Dicyanamide-hydroxypyridine Complexes

Zheng

2013

Journal of Inorganic Chemistry

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Three two-dimensional (2D) and 3D supramolecular coordination architectures based on ternary M(II)-dicyanamide-2-hydro- (2), and [Mn(hepH) 2 (dca) 2 ] (3) (dca = dicyanamide, hmpH = 2-(hydroxymethyl)pyridine, hepH = 2-(hydroxyethyl)pyridine), have been synthesized. 1 is a mononuclear Co(II) complex. The mononuclear units are interlinked into a 2D (4,4) hydrogen-bonded layer via O-H⋅ ⋅ ⋅ N hydrogen bonds between the hydroxyl groups and the noncoordinating nitrile ends. These 2D layers are further extended into a 3D supramolecular architecture via the interlayer pyridyl-pyridyl stacking interaction. 2 has a 1D coordination chain structure formed by the double 1,5 -dca bridged dinuclear [Cu2( 1,5 -dca) 2 (hmpH) 2 ] unit and the 1,3 -dca bridges via weak Cu-N coordination, and these 1D coordination chains are further extended into 2D hydrogen-bonded layers via strong O-H⋅ ⋅ ⋅ N hydrogen-bonding interaction between the hydroxyl groups and the noncoordinating nitrile ends. 3 is a 2D (4,4) coordination network made of 1D [Mn(hepH)( 1,5 -dca)] helical chain units and interchain double ( 1,5 -dca) bridges. Pairs of [Mn(hepH)( 1,5 -dca)] helical chains are interlinked by the double ( 1,5 -dca) bridges into a racemic coordination layer structure, which is further extended into a 3D hydrogen-bonded network. Magnetic studies reveal that weak antiferromagnetic exchange occurs in 3.

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“…19 The dca and tcm anions, along with the related carbamoyldicyanomethanide anion (cdm, [C(CN) 2 (CONH 2 )] -), readily undergo nucleophilic addition to a nitrile group, providing a convenient means of in situ ligand synthesis in the formation of transition metal complexes. [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.…”

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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Ferromagnetic Coupling Promoted by κ³N:κ²N Bridging System

Cited by 23 publications

References 25 publications

[N-(1-Azanidyl-2,2,2-trichloroethylidene)-2,2,2-trichloroethanimidamide]copper(II)

[N-(1-Azanidyl-2,2,2-trichloroethylidene)-2,2,2-trichloroethanimidamide]copper(II)

Synthesis, Crystal Structures, and Magnetic Properties of Ternary M(II)-Dicyanamide-hydroxypyridine Complexes

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

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