Thermal decomposition of the tris (2,2′-bipyridine) complexes of some first row transition group elements in the solid state

Dhar, S.K.; Basolo, Fred

doi:10.1016/0022-1902(63)80206-7

Cited by 27 publications

(7 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Moreover, the activation energies for the decomposition of nickel(II) N-alkyldithiocarbamates were found to 9 be comparable with the values previously reported for the square-planar d 8 metal(II) dithio complexes [7,18]. These values are also comparable with the values generally observed for four-coordinated transition metal complexes [19]. Finally, the positive values of entropies of activation indicate that the activated complexes have less ordered structures than the reactants.…”

Section: Decomposition Kineticssupporting

confidence: 85%

Kinetic analysis of thermogravimetric data on some nickel(II) N-alkyldithiocarbamates

Lalia‐Kantouri

Katsoulos

Hadjikostas

et al. 1989

Journal of Thermal Analysis

View full text Add to dashboard Cite

Thermogravimetric and derivative thermogravimetric curves of some complexes [Ni(S2CNHR)2] (R = Me, Et, Pr i, Bu i, Bu t, Bz, p:MePh, p-MeOPh, p-C1Ph, p-NO2Ph) in a dynamic nitrogen atmosphere were studied to determine their modes of decomposition. All these complexes show similar TG profiles. The weight losses in the main decomposition stages indicate conversion of the nickel(II) dithiocarbamates to sulphide. Reaction orders were estimated via the shape characteristics of the corresponding derivative thermogravimetric curves and kinetic analysis of the thermogravimetric data was performed by using the Coats-Redfern and Horowitz-Metzger methods.Dithiocarbamates constitute a class of organo-sulphur compounds with strong binding properties, which are also known to have profound effects on biological systems [1]. Interest in the study of metal dithiocarbamato complexes has been stimulated by their use in industry as vulcanization accelerators and as highpressure lubricants, whereas their use as fungicides and pesticides has induced a vast number of biological and biochemical investigations [2]. In this respect, several d 8 metal complexes of aliphatic and aromatic dithiocarbamates have already been studied in our laboratory in an attempt to establish the chemical and electronic properties of the various coordination geometries obtainable within the dithio-acid system [3 6]. One logical extension of this work was to study the thermal decomposition of bis(N-monosubstituted-dithiocarbamato)metal(II) complexes, [M(S2CNHR)2] (M = Ni, Pd, Pt), as a literature survey revealed that little work has been carried out on thermal studies of metal(II) N-alkyldithiocarbamates [7]. To this end, thermoanalytical data (TG and DTG) on some typical square-planar Ni(II) dithiocarbamates with substituents displaying various electronic effects are reported in the present paper. Moreover, an interpretation and numerical analysis of these data is attempted, since thermogravimetric analysis is an important method John W~ile.l~ & Sons, Limited, Chichester Akad~miai Kiad6; Budapest

show abstract

Section: Decomposition Kineticssupporting

confidence: 85%

Kinetic analysis of thermogravimetric data on some nickel(II) N-alkyldithiocarbamates

Lalia‐Kantouri

Katsoulos

Hadjikostas

et al. 1989

Journal of Thermal Analysis

View full text Add to dashboard Cite

show abstract

“…These values are comparable to the values generally observed for tetraco-ordinated transition metal complexes reported in literature and are somewhat lower than those for hexaco-ordinated complexes [10].…”

Section: Decomposition Kineticssupporting

confidence: 92%

Thermal decomposition kinetics of diethyl dithiocarbamate complexes of copper(II) and nickel(II)

Madhusudanan

Yusuff

Nair

1975

Journal of Thermal Analysis

View full text Add to dashboard Cite

Thermogravimetric (TG), derivative thermogravimetric (DTG) and differential thermal analysis (DTA) curves of CuL~ and NiL2 (L-= diethyl dithiocarbamate anion) in air are studied. The main decomposition temperature ranges are: For CuL2, DTG 250--350 ~ DTA 300--320 ~ and for NIL2, DTG 290--390 ~ DTA 360--400 ~ Mass loss considerations at the main decomposition stages indicate conversion of the complex to sulphides. Mathematical analysis of TG data shows that first order kinetics are applicable in both cases. Kinetic parameters (energy and entropy of activation and preexponential factor) are reported.Transition metal dithiocarbamates have important technical applications, for example, as vulcanization accelerators, as fungicides, etc. As part of an investigation on the thermal decomposition of transition metal complexes [1 ], we have now studied the dithiocarbamate complexes. Thermoanalytical data (TG, DTG and DTA) of two typical complexes, i.e., diethyl dithiocarbamato complexes of copper(ll) and nickel(II) are presented in this communication. Interpretation and mathematical analysis of these data and evaluation of order of reaction and the energy and entropy of activation, based on the differential method employing the Freeman-Carroll equation [2], the integral method using the Coats-Redfern equation [3] and the approximation method using the Horowitz-Metzger equation [4] are also given. Experimental Preparation of samplesSamples of diethyl dithiocarbamato copper(II) and diethyl dithiocarbamato nickel(II) [hereafter abbreviated as CuL2 and NiL2 respectively, where L = = (C2Hs)2NCS2] were prepared by adding, at room temperature (30~ 0.l M aqueous solutions of copper(H) sulphate and nickel(II) sulphate respectively to 0.1 M solutions of sodium diethyl dithiocarbamate. An excess of the ligand was employed (molar ratio, ligand/metal = 4). The precipitates were filtered, washed thoroughly with water, then with alcohol and dried in a vacuum desiccator.

show abstract

“…Concentration of the electrolyte did not have a major impact on the reaction despite the apparent voltage difference (entry 10, terminal potential 3–4 V for 0.2 M vs 4–6 V for 0.05 M). Finally, it was found that Ni(bpy) 3 Br 2 ( 17 ), a bench-stable and free-flowing solid with no apparent hygroscopicity, was an ideal precatalyst, which improved operational simplicity of this reaction by removing the need for the preparing stock solutions of hygroscopic NiBr 2 ·3H 2 O (entry 11). The preparation of this known precatalyst is exceedingly simple as illustrated in Table C and is currently being commercialized (Sigma-Aldrich ALD00608).…”

Section: Optimizationmentioning

confidence: 98%

Electrochemically Driven, Ni-Catalyzed Aryl Amination: Scope, Mechanism, and Applications

et al. 2019

View full text Add to dashboard Cite

C–N cross-coupling is one of the most valuable and widespread transformations in organic synthesis. Largely dominated by Pd- and Cu-based catalytic systems, it has proven to be a staple transformation for those in both academia and industry. The current study presents the development and mechanistic understanding of an electrochemically driven, Ni-catalyzed method for achieving this reaction of high strategic importance. Through a series of electrochemical, computational, kinetic, and empirical experiments, the key mechanistic features of this reaction have been unraveled, leading to a second generation set of conditions that is applicable to a broad range of aryl halides and amine nucleophiles including complex examples on oligopeptides, medicinally relevant heterocycles, natural products, and sugars. Full disclosure of the current limitations and procedures for both batch and flow scale-ups (100 g) are also described.

show abstract

Thermal decomposition of the tris (2,2′-bipyridine) complexes of some first row transition group elements in the solid state

Cited by 27 publications

References 12 publications

Kinetic analysis of thermogravimetric data on some nickel(II) N-alkyldithiocarbamates

Kinetic analysis of thermogravimetric data on some nickel(II) N-alkyldithiocarbamates

Thermal decomposition kinetics of diethyl dithiocarbamate complexes of copper(II) and nickel(II)

Electrochemically Driven, Ni-Catalyzed Aryl Amination: Scope, Mechanism, and Applications

Contact Info

Product

Resources

About