Anion dependence of ring conformational equilibriums of the tris(ethylenediamine)nickel(II) cation. 2. Effect of anion base strength in aqueous solution

Cramer, Roger E.; Huneke, James T.

doi:10.1021/ic50179a013

Cited by 8 publications

(8 citation statements)

References 23 publications

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“…A common feature for both is that iodide anions are bonded to -NH(ob) groups, in agreement with the steric criterion of Raymond, Corfield & Ibers (1968) developed by Spinat, Whuler & Brouty (1979). On the other hand, it can be assumed that the presence of four base sites in the planar oxalate anions makes possible the stabilization of A666 or A222 configurations instead of other configurations, such as A2,;t2 or A66~, which are usually stabilized when an extensive hydrogen-bonding network exists (Haque, Caughlan & Emerson, 1970;Duesler & Raymond, 1971;Cramer & Huneke, 1978).…”

Section: Experimental Suitable Rectangular Prismatic Crystalsmentioning

confidence: 99%

Structure of the active racemic complex [(±)Co(en)3](C2O4)I.1.5H2O: a hydrogen-bond-induced case of asymmetry

Fuertes¹,

Miravitlles²,

Ibáñez³

et al. 1988

Acta Crystallogr C

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Section: Experimental Suitable Rectangular Prismatic Crystalsmentioning

confidence: 99%

Structure of the active racemic complex [(±)Co(en)3](C2O4)I.1.5H2O: a hydrogen-bond-induced case of asymmetry

Fuertes¹,

Miravitlles²,

Ibáñez³

et al. 1988

Acta Crystallogr C

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“…I1 est admis que les liaisons hydrog6ne (Tableau 7) jouent un r61e d6terminant fi l'6tat cristallin, sur la stabilisation d'un ion complexe [M(en)a] 3+, dans une conformation donn6e (Raymond, Corfield & Ibers, 1968b;Cramer & Huneke, 1978). II est toutefois difficile de cerner les crit6res pr6cis permettant d'6tablir la corr61ation entre liaisons H et conformation.…”

Section: Liaandons Hydrog~ne Et Conformation Des Ions Complexesunclassified

Etude structurale du bromure de tris(éthylènediamine)chrome(III) 0,6 hydraté, (+)-[Cr(en)3]Br3.0,6H2O

Spinat¹,

Whuler²,

Brouty³

1979

Acta Crystallogr Sect B

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The structure can be described as consisting of complex-ion layers P(1) P(2) P(1)...; P(1) layers are formed by a lattice of elementary pentagonal and triangular figures. The ieosahedral holes defined by this stacking are occupied by the other complex ions lying in P(2) layers. The same type of arrangement can be observed in three dimensions and so confers a pseudocubic character on this orthorhombic structure. IntroductionS'il existe une isotypie totale (maille commune trigonale subissant peu de variations de param&res) entre les cristaux rac6miques des complexes [M(en)3]X 3 (M = Co IiI, Cr m, Rh met X = CI-, Br-) (Whuler, Brouty, Spinat & Herpin, 1975, il n'en est plus de m~me en ce qui concerne leurs cristaux actifs. Ces derniers se caract6risent, en effet, ~ l'int6rieur d'une m~me s6rie X-, par des structures cristallines totalement diff~r-entes: (+)-[Co(en)a]Cl3.H20 est quadratique (Iwata, Nakatsu & Saito, 1969), (+)-[Cr(en)a]Cl3.2H20 monoclinique et (-)-[Rh(en)3]C13 cubique (Whuler, 1978). Par contre, les r6sultats obtenus par Nakatsu (1962) et Iwata et al. (1969) L'&ude des param&res cristallins conduit ~ une maille 61~mentaire de sym&rie orthorhombique (Spinat, Whuler & Brouty, 1979). Le groupe de sym6trie est P21212 ~ conform6ment aux r+flexions observ~es h00, h = 2n, 0k0, k = 2n, et 00l, l = 2n, et ~ l'activit+ optique du cristal. I1 apparait d6s lors que la maille cristalline de (+)-[Cr(en)3lBr a diff6re totalement de celle obtenue D~termination structuraleLes facteurs de diffusion utilis6s sont calcul6s ~ partir des tables de coefficients publifs par Cromer & Mann (1968), en tenant compte de la diffusion anomale des atomes de chrome (f' = 0,3 etf" = 0,75) et de brome (f' = -0,3 etf"= 2,5).La structure est r6solue par m6thodes directes, /t raide du programme MULTAN (Germain, Main & Woolfson, 1971 (Spinal et al., 1979). Ce ph6nom6ne a pu &re observ6 sur r6chantillon utilis6 pour les mesures diffractom&riques, sans aucune destruction du monocristal. Cependant il est 6vident que les mesures d'intensit6s de la phase orthorhombique etudi/~e ici, doivent &re sensiblement perturb6es par cette lente 6volution cristalline.Le Tableau 1 r6capitule l'ensemble des coordonn6es atomiques de la structure ainsi que les facteurs d'agitation thermique de chaque atome (B ou B moyen).* Description structurale Les ions complexesLa projection de la structure effectu6e sur le plan (100) (Fig. 1) Fig. 1. Projection de ia structure I (100).2916 (18) 2816 (22) 2262 (26) 3,4 (0,6) H'(C61) 44 501 83 577 (18) 5464 (23) 1171 (26) (12) 148 (15) 3684 (18) 2,1 (0,5) H'(N22) 249 20 331 3170 (12) 1070 (15) 4589 (17) 2,0 (0,5) H(N32) 296 151 445 1997 (12) -844 (15) 5268 (17) 1,9 (0,5) H'(N32) 339 91 414 1775 (11) 961 (13) 5163 (15) 1,4 (0,4) H(N42) 162 -79 502 2884 (11) 325 (14) 6195 (16) (15) 906 (18) 4463 (22) 2,0 (0,5) H(C12) 308 -147 577 3224 (14) 1175 (17) 6221 ( (14) 2721 (17) 3388 (20) L'orientation mutuelle des trois ions complexes ind,-pendants peut se d6finir de faqon simple en rep6rant l'angle 09 que fait leur pseudoaxe ...

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“…The minor differences can be attributed to the fact that the calculated values have been obtained for the gas phase while the corresponding experimental values are for the solid state [19]. While calculating the conformational pathways, it was found that variations of two dihedral angles, H-N-Ni-X (D2) and H-C-N-H (D5) were required.…”

Section: Transition State Pathwaysmentioning

confidence: 99%

Conformational stabilities, EPR, IR and VCD studies of Tris(ethylenediamine)nickel(II) chloride

Noorani

Rahemi

Tayyari

2010

JICS

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Conformational stabilities of the transition metal complex of the [Ni(en) 3 ]Cl 2 was studied using Density Functional Theory (DFT). The deformational potential energy profiles (PEPS), pathways between the different isomeric conformational energies were calculated using B3LYP/6-31G. Relative conformational energies of the Δ(λλλ), Δ(λλδ), Δ(λδδ) and Δ(δδδ) were 0.04, 0.36, 0.17, 0.0 kcal mol -1 , respectively, which were small compared to the barrier heights for the reversible phase transitions 51.12, 50.48, 49.64 kcal mol -1 , respectively. The frequency assignment was carried out by fitting Fourier transform infrared (FTIR) spectra and using Gaussian and GaussView computer programs. The theoretical vibrational circular dichroism (VCD) absorption spectra are presented for all conformations in the range of 400-3500 cm -1 . Calculated electron paramagnetic resonance (EPR) gtensor parameters of the [Ni(en) 3 ]Cl 2 , g x = 2.69, g y = g z = 2.71, are well compared to the corresponding experimental values and indicate a spherical electronic structure for the Ni atom in this compound.

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Anion dependence of ring conformational equilibriums of the tris(ethylenediamine)nickel(II) cation. 2. Effect of anion base strength in aqueous solution

Cited by 8 publications

References 23 publications

Structure of the active racemic complex [(±)Co(en)3](C2O4)I.1.5H2O: a hydrogen-bond-induced case of asymmetry

Structure of the active racemic complex [(±)Co(en)3](C2O4)I.1.5H2O: a hydrogen-bond-induced case of asymmetry

Etude structurale du bromure de tris(éthylènediamine)chrome(III) 0,6 hydraté, (+)-[Cr(en)3]Br3.0,6H2O

Conformational stabilities, EPR, IR and VCD studies of Tris(ethylenediamine)nickel(II) chloride

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