The Crystal Structure of Nitropentamminecobalt(III) Chloride, [CoNO2(NH3)5]Cl2.

Börtin, Olle; Johansson, Georg; Sandberg, F; Norin, Torbjörn

doi:10.3891/acta.chem.scand.22-2890

Cited by 24 publications

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“…It can bind to the metal through N as well as through O, leading to linkage isomerism. The ambident reactivity of the nitrite ion was studied in detail by Tishkov et al 10 For instance, the cationic cobalt complex of formula [Co(NH 3 ) 5 NO 2 ]Cl 2 exists as either the yellow-colored nitro isomer ([Co(NH 3 ) 5 NO 2 ]Cl 2 ), where the nitro ligand is bound to Co through nitrogen, or the red-colored nitrito isomer ([Co(NH 3 ) 5 ONO]Cl 2 ), where the nitrito is bound to Co through one of the oxygen atoms [11][12][13][14][15][16] Several research groups have focused their studies on metal linkage compounds due to their potential applications in medicinal therapy, photo-responsive materials, tunable optical materials, and molecular devices. [11][12][13][17][18][19][20][21][22][23][24][25][26] The transformation of the N-bonded nitro isomer to the less stable O-bonded nitrito isomer has already been extensively studied experimentally and the conversion was demonstrated to occur intramolecularly.…”

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confidence: 99%

Theoretical investigation on the ground state properties of the hexaamminecobalt(iii) and nitro–nitrito linkage isomerism in pentaamminecobalt(iii) in vacuo

2018

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Section: Introductionmentioning

confidence: 99%

Theoretical investigation on the ground state properties of the hexaamminecobalt(iii) and nitro–nitrito linkage isomerism in pentaamminecobalt(iii) in vacuo

2018

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“…Numerous studies have investigated the photoisomerization behavior of [Co(NH) 5 NO 2 ] 2+ surrounded by inorganic anions . The solid state isomerization occurs intramolecularly through the NO bond and is accompanied by an increase in molar volume .…”

Section: Introductionmentioning

confidence: 99%

“…The solid state isomerization occurs intramolecularly through the NO bond and is accompanied by an increase in molar volume . The nitrito isomers of [Co(NH 3 ) 5 ONO](NO 3 ) 2 , [Co(NH 3 ) 5 ONO]Br 2 , [Co(NH 3 ) 5 ONO]Cl 2 , [Co(NH 3 ) 5 ONO](NO 3 )Cl, and [Co(NH 3 ) 5 ONO](ClO 4 ), when stored in the dark in ambient conditions, undergo slow spontaneous transformations into the corresponding nitro isomers . The base dependence and pressure dependence of this linkage isomerization has been studied .…”

Section: Introductionmentioning

confidence: 99%

“…Numerous studies have investigated the photoisomerization behavior of [Co(NH) 5 NO 2 ] 2+ surrounded by inorganic anions. [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] The solid state isomerization occurs intramolecularly through the N O bond [8][9][10] and is accompanied by an increase in molar volume. [11,13,19] The nitrito isomers of [Co(NH 3 ) 5 ONO](NO 3 ) 2 , [Co(NH 3 ) 5 ONO]Br 2 , [Co(NH 3 ) 5 ONO]Cl 2 , [Co(NH 3 ) 5 ONO](NO 3 )Cl, and [Co(NH 3 ) 5 ONO](ClO 4 ), when stored in the dark in ambient conditions, undergo slow spontaneous transformations into the corresponding nitro isomers.…”

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confidence: 99%

“…[11,13,19] The nitrito isomers of [Co(NH 3 ) 5 ONO](NO 3 ) 2 , [Co(NH 3 ) 5 ONO]Br 2 , [Co(NH 3 ) 5 ONO]Cl 2 , [Co(NH 3 ) 5 ONO](NO 3 )Cl, and [Co(NH 3 ) 5 ONO](ClO 4 ), when stored in the dark in ambient conditions, undergo slow spontaneous transformations into the corresponding nitro isomers. [6][7][8][9][10][11][12]21,22] The base dependence and pressure dependence of this linkage isomerization has been studied. [16] Experiments providing detailed information on the synthesis of [Co(NH 3 ) 5 NO 2 ] 2+ and [Co(NH 3 ) 5 ONO] 2+ in various inorganic environments have been reported elsewhere.…”

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A theoretical insight into the role of counter anions and their interactions in nitropentaamminecobalt(III) toward linkage isomerism‐induced photochemical motion

Muya

Meher

Sahoo

et al. 2019

Int J of Quantum Chemistry

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Density functional theory (B3LYP, B3LYP‐D3, wB97XD, M062X, and M06L) and ab initio methods (MP2 and CCSD(T)) in conjunction with 6‐31+G(d,p) and LanL2DZ were employed to investigate the interaction energies between [Co(NH3)5NO2]2+ linkage isomers and chloride and nitrate in both gas phase and solid state. The nature of the chemical bonding has been analyzed by means of the atoms in molecules, electron density shift, natural bond orbitals, symmetry adapted perturbation theory, and energy decomposition analysis. The electronic structures of the two lowest laying singlet states (So and S1) of [Co(NH3)5NO2](NO3)Cl isomers were also investigated using CASSCF(6,6) with LanL2DZ and 6‐31G(d) basis sets. Our results show that [Co(NH3)5NO2]2+ linkage isomers interact more strongly with chloride than nitrate. The structures of [Co(NH3)5NO2](NO3)Cl linkage isomers and their relative stabilities were examined in gas phase and in solid state and confirmed the nitro‐complex as the most stable following by a viable intermediate endo‐complex. Study of the nitro‐nitrito linkage isomerization in [Co(NH3)5NO2](NO3)Cl revealed that anions form strong electrostatic bonds with [Co(NH3)5NO2]2+ leading to decrease in an activation energy compared to the [Co(NH3)5ONO]2+ isomers. A concerted action of ionic interactions and hydrogen bonds are suspected of regulating the isomerization in solid state. Assessment of various DFT methods with respect to CCSD(T) suggests M062X suitable method for [Co(NH3)5NO2](NO3)Cl linkage‐isomerization study. Potential energy surface calculations at the CASSCF/6‐31G(d) level of theory shows that the conical intersection (S1/So) might play an important role in the photoisomerization of [Co(NH3)5NO2](NO3)Cl.

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Effect of high pressure on the infrared spectra of solid nitro‐ and nitrito‐cobalt(iii) ammine complexes

Болдырева

Burleva

Burgina

et al. 1992

Ber Bunsenges Phys Chem

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Complex Compounds / Crystal Structure 1 High Pressure 1 Spectroscopy, Infrared IR-absorption spectra of Co(II1) ammine complexes [CO(NH~)~NO~]XY and [Co(NH,),ONO]XY (XY = CI2, Br2, 12, (N03)2, CI . NO3) were studied at static pressures up to 20 kbar in a diamond anvil cell. The measured pressure induced shifts of valence (symmetric and asymmetric) and deformational frequencies of the N02-group were compared with a normal coordinate analysis of [ C O ( N H~)~N O~]~+ and [CO(NH~)~ONO]~+ models to determine the influence of kinematic factors on IR-vibrational frequencies.The experimentally observed frequency shifts induced by pressure were interpreted on the basis of theoretical simulation of the spectra. The blue shift of both &NO2) and vas(ONO) vibrational frequencies in the complexes with nitro (via nitrogen) coordination can be explained by a decrease in N -0 bond lengths. The blue shift of v'(0NO) and the red shift of vas(ONO) frequencies in the solid complexes with nitrito (via oxygen) coordination can be explained by a decrease of the 0 -N -0 bond angle with increasing pressure. For comparison, the pressure induced shifts of v'(ON0) and vaS(ONO) for two Cr(II1)-ammine complexes [Cr(NH3)sONO]XY (XU = CI2, (NOJ)2) were also measured. Whereas the pressure dependence of vs is similar to the corresponding Co-compounds, vas is only slightly pressure dependent.

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The Crystal Structure of Nitropentamminecobalt(III) Chloride, [CoNO2(NH3)5]Cl2.

Cited by 24 publications

References 0 publications

Theoretical investigation on the ground state properties of the hexaamminecobalt(iii) and nitro–nitrito linkage isomerism in pentaamminecobalt(iii) in vacuo

Theoretical investigation on the ground state properties of the hexaamminecobalt(iii) and nitro–nitrito linkage isomerism in pentaamminecobalt(iii) in vacuo

A theoretical insight into the role of counter anions and their interactions in nitropentaamminecobalt(III) toward linkage isomerism‐induced photochemical motion

Effect of high pressure on the infrared spectra of solid nitro‐ and nitrito‐cobalt(iii) ammine complexes

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