Copper(I) nitrate π-complexes. Synthesis and crystal structure of CuNo3(CH2=CH-CH2)2NCN

Olijnik, V. V.; Goreshnik, Evgeny; Mys’kiv, М. G.; Pecharskii, V. K.

doi:10.1007/bf02578505

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“…The degree of the geometry distortion is greater for the dihydrate (geometry index [23] [22,27,30], and the solvates Cu4X6O(NCNMe2)4•4(arene) (X = Cl, Br; arene = PhMe, PhCH=CH2) [22], and no single example of mononuclear (NCNR2)Cu II was known. For copper(I), there are several known structures of mononuclear complexes [Cu(NCNR2)4](BF4) [20], [Cu(tpm)(NCNR2)](BF4) (tpm = tris-(1,3-dimethylpyrazolyl)methane) [21], and [Cu(NCNMe2)2(DPEphos)](BF4) [32], and polymeric [CuX(NCNAllyl2)] (X = Cl, Br, NO3) species [33].…”

Section: X-ray Diffraction Studiesmentioning

confidence: 99%

“…The (N-sac)2Cu II moiety is rather typical for various saccharinate complexes. [32], and polymeric [CuX(NCNAllyl 2 )] (X = Cl, Br, NO 3 ) species [33].…”

Section: X-ray Diffraction Studiesmentioning

confidence: 99%

“…Structures of cyanamide copper(II) complexes were previously represented by the clusters Cu4Cl6O(NCNR2)4 (R = Me, allyl)[22,27,30], and the solvates Cu4X6O(NCNMe2)4•4(arene) (X = Cl, Br; arene = PhMe, PhCH=CH2)[22], and no single example of mononuclear (NCNR2)Cu II was known. For copper(I), there are several known structures of mononuclear complexes [Cu(NCNR2)4](BF4)[20], [Cu(tpm)(NCNR2)](BF4) (tpm = tris-(1,3-dimethylpyrazolyl)methane)[21], and [Cu(NCNMe2)2(DPEphos)](BF4)(DPEphos = bis[2 -diphenylphosphino)phenyl]-ether) [31], dinulear [Cu2(μ2-Cl)2(dppm)2(NCNMe2)]•2NCNMe2, [Cu2(μ2-Cl)(dppm)2(NCNMe2)](Cl), [Cu2(μ2-X)(dppm)2(NCNMe2)2](X) (X = ClO4, NO3), [Cu2(dppm)2(NCNMe2)3](BF4)2[32], and polymeric [CuX(NCNAllyl2)] (X = Cl, Br, NO3) species[33].On the other hand, these complexes represent examples of the (N-sac)2Cu II -type complexes. Metal complexes of saccharin(ate) exhibit versatile coordination chemistry due to the existence of different coordination sites[34].…”

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confidence: 99%

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Copper(II) Prevents the Saccarine-Dialkylcyanamide Coupling by Forming Mononuclear (Saccharinate)(Dialkylcyanamide)copper(II) Complexes

Toikka¹,

Spiridonova²,

Novikov³

et al. 2021

Inorganics

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The reaction in the system CuII/sacNa(H)/NCNR2 (sacNa(H) = sodium saccharinate (saccharin); R = Me, Et) results in the formation of the complexes [Cu(sac)2(NCNR2)(H2O)2] (R = Me 1, Et 2) instead of the expected products derived from the saccharin–cyanamide coupling. Complexes 1, 2, and hydrate 1·2H2O were characterized by IR, AAS (Cu%), TGA, and also by single-crystal X-ray diffraction for 1 and 1·2H2O. An integrated computational study of model structure 1 in the gas phase demonstrates that the Cu–Ncyanamide and Cu–Nsac coordination bonds exhibited a single bond character, polarized toward the N atom and almost purely electrostatic, with the calculated vertical total energies for the Cu–Ncyanamide and Cu–Nsac of 43.6 and 156.4 kcal/mol, respectively. These data confirmed that the copper(II) completely blocks the nucleophilic centers of ligands via coordination, thus preventing the saccharin–cyanamide coupling.

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Section: X-ray Diffraction Studiesmentioning

confidence: 99%

“…The (N-sac)2Cu II moiety is rather typical for various saccharinate complexes. [32], and polymeric [CuX(NCNAllyl 2 )] (X = Cl, Br, NO 3 ) species [33].…”

Section: X-ray Diffraction Studiesmentioning

confidence: 99%