Kinetics of tetracyanonickelate(II) reactions

Crouse, Walter C.; Margerum, Dale W.

doi:10.1021/ic50136a036

Cited by 14 publications

(7 citation statements)

References 24 publications

(10 reference statements)

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“…5). The spectral properties of TCN were found to be consistent with those reported previously (4,13,24). Its purity was estimated to be about 95% from absorbance measurements made with aqueous solutions.…”

supporting

confidence: 88%

Degradation of the metal-cyano complex tetracyanonickelate(II) by cyanide-utilizing bacterial isolates

Silva-Avalos

Richmond

Nagappan

et al. 1990

Appl Environ Microbiol

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Ten bacterial isolates capable of growth on tetracyanonickelate(II) {K2[Ni(CN)4]} (TCN) as the sole nitrogen source were isolated from soil, freshwater, and sewage sludge enrichments. Seven of the 10 were identified as pseudomonads, while the remaining 3 were classified as Klebsiella species. A detailed investigation of one isolate, Pseudomonas putida BCN3, revealed a rapid growth rate on TCN (generation time, 2 h), with substrate removal and growth occurring in parallel. In addition to TCN, all isolates were able to utilize KCN, although the latter was significantly more toxic; MICs ranged from 0.2 to 0.8 mM for KCN and .50 mM for TCN. While growth occurred over a wide range of TCN concentrations (0.25 to 16 mM), degradation was most substantial under growth-limiting conditions and did not occur when ammonia was present. In addition, cells grown on TCN were found to accumulate nickel cyanide [Ni(CN)21 as a major biodegradation product. The results show that bacteria capable of growth on TCN can readily be isolated and that degradation (i) appears to parallel the capacity for growth on KCN, (ii) does not occur in the presence of ammonia, and (iii) proceeds via the formation of Ni(CN)2 as a biological metabolite.

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supporting

confidence: 88%

Degradation of the metal-cyano complex tetracyanonickelate(II) by cyanide-utilizing bacterial isolates

Silva-Avalos

Richmond

Nagappan

et al. 1990

Appl Environ Microbiol

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“…Molybdenum complexes studied here are the six complexes Mo04_"S"2" (« = 0-4) and MoSe42". The experimental data of the chemical shifts for these complexes are reported in water and CH3CN solution by Lutz et al 4 and by Gheller et al 5 As they mentioned, the effect of replacing a hard ligand (oxygen) with a softer one (sulfur and selenium) is quite interesting in that it causes a regular change in the chemical shift.…”

Section: Methodsmentioning

confidence: 94%

Theoretical study on the metal NMR chemical shift. Molybdenum complexes

Nakatsuji¹,

Sugimoto²

1990

Inorg. Chem.

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The 95Mo NMR chemical shift of the molybdenum complexes Mo04_"X"2-(X = S, Se; = 0-4) is studied theoretically with the ab initio molecular orbital method. The calculated results are in quite good agreement with experiments, showing the reliability of the method used in this series of studies. The Mo chemical shift mainly reflects the change in the valence 4d orbitals of molybdenum caused by ligand substitution. A perturbation theoretical analysis reveals that this change is dictated by the stabilization of the unoccupied Ada* and 4drr* orbitals by the participation of the ligand orbitals. We then predict that the Mo chemical shift will increase as the softness of the ligand increases. This trend is somewhat similar to that of the Mn chemical shift studied previously. We further predict inverse proportionality between the magnetically allowed d-d transition energy and the Mo chemical shift.

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“…NiL2~" + CN" NiLÍCN)1-" (rapid) (7) Ni(CN)1-" + CN' J=± NiL(CN)2-n (rapid) (8) NiL(CN)2-" + CN" NiL(CN)3-(,l+1) (rds) (9) R-3 The application of the steady state approximation to NiL(CN)3-(n+1) in the postulated mechanism gives the following rate equation for the reverse reaction:…”

Section: Discussionmentioning

confidence: 99%

Kinetics and mechanism of tetracyanonickelate formation. 1. From mono(aminocarboxylate)nickel(II) complexes

Kumar¹,

Nigam²,

Pandey³

1978

J. Phys. Chem.

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The kinetics and mechanism of the system NiL2"" + 4CN~" Ni(CN)42" + L"", where L = DTPA (diethylenetriaminepentaacetic acid) and PDTA (1,2-diaminopropanetetraacetic acid), have been investigated. The reaction conditions are pH 11.0 ± 0.2, µ = 0.1 M and t = 25 ± 0.1 °C. As in the reaction of Ni(II)-EDTA2ã nd Ni(II) complexes of other aminocarboxylates reported earlier, the formation of mixed ligands of the type NiLCCN)*2""'1'"* was verified. The transition between NiL2"" and Ni(CN)42" is kinetically controlled by the presence of three cyanide ions around one nickel atom in the rate-determining step. The reaction rates are convenient to follow spectrophotometrically. Both reactions are first order in NiL2"". A variable dependence on cyanide ion concentration (always present in large excess) is observed. The reverse reaction rates are first order in Ni(CN)42" concentration, first order in L"", and inverse first order in cyanide ion concentration. The first-order forward rate constants (in cyanide dependence) k3 are (3.27 ± 0.22) X 10"1 and (5.70 ± 0.8) X 10"3 M"1 s"1; second-order rate constants K2k3 are (5.53 ± 0.77) and (1.77 ± 0.12) X 10"2 M"2 s"1 for DTPA and 1,2-PDTA, respectively. The reverse rate constants kT = (A4"1/z_3) for these two reactions are (4.78 ± 0.6) X 10"8 and (3.03 ± 0.24) X 10"9 s"1, respectively. From the investigation of the pH dependence of reaction rate over the pH range 7-11, it is inferred that one molecule of HCN is involved in the reaction in addition of two CN" upto the rate-determining step between pH 7.0 and 9.0.

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Kinetics of tetracyanonickelate(II) reactions

Cited by 14 publications

References 24 publications

Degradation of the metal-cyano complex tetracyanonickelate(II) by cyanide-utilizing bacterial isolates

Degradation of the metal-cyano complex tetracyanonickelate(II) by cyanide-utilizing bacterial isolates

Theoretical study on the metal NMR chemical shift. Molybdenum complexes

Kinetics and mechanism of tetracyanonickelate formation. 1. From mono(aminocarboxylate)nickel(II) complexes

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