Ligand substitution and redox properties of 4-picolylaminepentacyanoferrate(II)

1986 ◽  
Vol 11 (6) ◽  
pp. 213-217 ◽  
Author(s):  
Patricia A. M. Williams ◽  
Pedro J. Aymonino
Keyword(s):  
Ligand Substitution ◽  
Redox Properties

Accessing relatively electron poor cerium(iv) hydrazido complexes by lithium cation promoted ligand reduction

2016 ◽  
Vol 45 (38) ◽  
pp. 15249-15258 ◽  
Author(s):  
Jessica R. Levin ◽  
Thibault Cheisson ◽  
Patrick J. Carroll ◽  
Eric J. Schelter
Keyword(s):  
General Formula ◽  
Ligand Substitution ◽  
Redox Properties ◽  
Lithium Cation

A series of substituted N,N′-diarylhydrazines (ArNHNHAr) were reacted with Ce(iii)[N(SiMe3)2]3 and LiN(SiMe3)2 to form complexes of general formula Li4(OEt2)4 [Ce(iv)(ArNNAr)4] where the spectroscopic and redox properties were affected by the ligand substitution.

scholarly journals Electronic Consequences of Ligand Substitution at Heterometal Centers in Polyoxovanadium Clusters: Controlling the Redox Properties through Heterometal Coordination Number

2020 ◽  
Vol 26 (44) ◽  
pp. 9905-9914 ◽  
Author(s):  
Rachel L. Meyer ◽  
Montaha H. Anjass ◽  
Brittney E. Petel ◽  
William W. Brennessel ◽  
Carsten Streb ◽  
...  
Keyword(s):  
Coordination Number ◽  
Ligand Substitution ◽  
Redox Properties

Synthesis and Photochemical Properties of Re(I) Tricarbonyl Complexes Bound to Thione and Thiazole-2-ylidene Ligands

2020 ◽  
Author(s):  
Matthew Stout ◽  
Brian Skelton ◽  
Alexandre N. Sobolev ◽  
Paolo Raiteri ◽  
Massimiliano Massi ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Excited States ◽  
Ligand Exchange ◽  
Ligand Substitution ◽  
Bidentate Ligand ◽  
The Other ◽  
Ligand Exchange Reaction ◽  
Multiple Products ◽  
Ligand Charge Transfer ◽  
Photochemical Properties

<p>Three Re(I) tricarbonyl complexes, with general formulation Re(N^L)(CO)<sub>3</sub>X (where N^L is a bidentate ligand containing a pyridine functionalized in the position 2 with a thione or a thiazol-2-ylidene group and X is either chloro or bromo) were synthesized and their reactivity explored in terms of solvent-dependent ligand substitution, both in the ground and excited states. When dissolved in acetonitrile, the complexes bound to the thione ligand underwent ligand exchange with the solvent resulting in the formation of Re(NCMe)<sub>2</sub>(CO)<sub>3</sub>X. The exchange was found to be reversible, and the starting complex was reformed upon removal of the solvent. On the other hand, the complexes appeared inert in dichloromethane or acetone. Conversely, the complex bound to the thiazole-2-ylidene ligand did not display any ligand exchange reaction in the dark, but underwent photoactivated ligand substitution when excited to its lowest metal-to-ligand charge transfer manifold. Photolysis of this complex in acetonitrile generated multiple products, including Re(I) tricarbonyl and dicarbonyl solvato-complexes as well as free thiazole-2-ylidene ligand.</p>

Outer-sphere interaction of (S)-asparagine and (S)-glutamine with [Co(NH3)6]3+ ion and its possible role in ligand substitution

1987 ◽  
Vol 52 (10) ◽  
pp. 2457-2459
Author(s):  
František Jursík
Keyword(s):  
Amino Acids ◽  
Transition Region ◽  
Alkaline Medium ◽  
Optical Activity ◽  
Substitution Reaction ◽  
Outer Sphere ◽  
Ligand Substitution ◽  
Cotton Effect ◽  
Negative Cotton Effect

Optical activity of the achiral cation [Co(NH3)6]3+ is induced both by (S)-AsnONa and (S)-GlnONa, as shown by a negative Cotton effect in the 1A1g → 1T1g transition region. An outer-sphere interaction by three-point attachment of the amides can explain the fact that substitution reaction of [Co(NH3)6]3+ with the mentioned amides in an alkaline medium is unusually slow as compared with other amino acids.

Polymer oxidation catalyst containing acidic functional groups

1981 ◽  
Vol 46 (5) ◽  
pp. 1237-1247
Author(s):  
Zdeněk Prokop ◽  
Karel Setínek
Keyword(s):  
Functional Groups ◽  
Elevated Temperatures ◽  
Redox Properties ◽  
Oxidation Catalyst ◽  
Carbon Clusters ◽  
Oxidation Activity ◽  
Redox Sites ◽  
Styrene Divinylbenzene ◽  
Proportional Decrease ◽  
Polymer Oxidation

The catalyst containing redox sites in addition to acid functional groups was prepared by sulphonation of a macroporous chloromethylated styrene-divinylbenzene copolymer with concentrated sulphuric acid at elevated temperatures. Its activity was tested for the oxidation of 2-propanol by molecular oxygen at 120 °C and was found to be comparable to that of the iridium on carbon catalyst.Neutralisation of acid functional groups by alkali metal led to proportional decrease in the oxidation activity. The results of EPR spectroscopic study of these catalysts show that the redox properties of the polymer are caused by carbon clusters which are capable of electron exchange.

Solvation and redox properties of [Co(en)3]3+-[Co(en)3]2+ system

1980 ◽  
Vol 45 (2) ◽  
pp. 335-338 ◽  
Author(s):  
Adéla Kotočová ◽  
Ulrich Mayer
Keyword(s):  
Hydrogen Bond ◽  
Lewis Acid ◽  
Specific Interaction ◽  
Redox Properties ◽  
Solvation Effect ◽  
Interacting Particles ◽  
Acid Base ◽  
Polar Solvents ◽  
Oxidation Reduction ◽  
Solvent Molecules

The solvation effect of a number of nonaqueous polar solvents was studied on the oxidation-reduction properties of the [Co(en)3]3+-[Co(en)3]2+ system. Interactions of these ions with the solvent molecules are discussed in terms of their coordination, which is accompanied by a specific interaction of the Lewis acid-base type, namely formation of a hydrogen bond between the interacting particles. This is the main controlling factor of the redox properties of the studied system.

Influence of Metal Core Composition on Redox Properties and Photoreactivity of the Clusters [H4-xRu4-xRhx(CO)12] (x = 0, 2, 3, 4)

2001 ◽  
Vol 66 (7) ◽  
pp. 1062-1077 ◽  
Author(s):  
Maarten J. Bakker ◽  
Tapani A. Pakkanen ◽  
František Hartl
Keyword(s):  
Electrochemical Properties ◽  
Electrochemical Reduction ◽  
Redox Properties ◽  
Metal Core ◽  
Loss Product ◽  
Condensation Reactions ◽  
Core Composition ◽  
Co Dissociation ◽  
Major Reduction

Electrochemical properties of tetrahedral clusters [H2Ru2Rh2(CO)12], [HRuRh3(CO)12] and [Rh4(CO)12] were investigated in order to evaluate the influence of metal core composition in the series [H4-xRu4-xRhx(CO)12] (x = 0-4). The cluster [H3Ru3Rh(CO)12] was not available in sufficient quantities. As reported for [H4Ru4(CO)12], electrochemical reduction of the hydride-containing clusters [H2Ru2Rh2(CO)12] and [HRuRh3(CO)12] also results in (stepwise) loss of hydrogen, producing the anions [HRu2Rh2(CO)12]-, [Ru2Rh2(CO)12]2- and [RuRh3(CO)12]-. These anions can also be prepared from the neutral parent clusters via chemical routes. Electrochemical reduction of [Rh4(CO)12] does not result in the formation of any stable tetranuclear anion. Instead, [Rh5(CO)15]- and [Rh6(CO)15]2- are the major reduction products detected in the course of IR spectroelectrochemical experiments. Most likely, these cluster species are formed from the secondary CO-loss product [Rh4(CO)11]2- by fast redox condensation reactions. Their reoxidation regenerates parent [Rh4(CO)12], together with some [Rh6(CO)16]. Unlike [H4Ru4(CO)12] that undergoes photochemical CO-dissociation, [H2Ru2Rh2(CO)12] and [Rh4(CO)12] are completely photostable in neat hexane and dichloromethane as well as in the presence of oct-1-ene.

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