The hexafluorooxotechnetate(2-) anion: the first example of a multiply charged, pentagonal bipyramidal, main-group element AX5YZ species and the vibrational spectra of the TeOF5- anion

1993 ◽  
Vol 32 (19) ◽  
pp. 4089-4093 ◽  
Author(s):  
Karl O. Christe ◽  
David A. Dixon ◽  
Jeremy C. P. Sanders ◽  
Gary J. Schrobilgen ◽  
William W. Wilson
Keyword(s):  
Vibrational Spectra ◽  
Main Group ◽  
Group Element ◽  
Multiply Charged ◽  
Main Group Element

Catalytic Fluorination of Boron Compounds at a Bismuth Redox Platform

2019 ◽  
Author(s):  
Oriol Planas ◽  
Feng Wang ◽  
Markus Leutzsch ◽  
Josep Cornella
Keyword(s):  
Transition Metal ◽  
Main Group ◽  
Group Element ◽  
Oxidation States ◽  
Boron Compounds ◽  
Main Text ◽  
Main Group Element ◽  
Rational Ligand Design ◽  
Supplementary Material

The ability of bismuth to maneuver between different oxidation states in a catalytic redox cycle, mimicking the canonical organometallic steps associated to a transition metal, is an elusive and unprecedented approach in the field of homogeneous catalysis. Herein we present a catalytic protocol based on bismuth, a benign and sustainable main-group element, capable of performing every organometallic step in the context of oxidative fluorination of boron compounds; a territory reserved to transition metals. A rational ligand design featuring hypervalent coordination together with a mechanistic understanding of the fundamental steps, permitted a catalytic fluorination protocol based on a Bi(III)/Bi(V) redox couple, which represents a unique example where a main-group element is capable of outperforming its transition metal counterparts.<br>A main text and supplementary material have been attached as pdf files containing all the methodology, techniques and characterization of the compounds reported.<br>

scholarly journals On the Coordination Role of Pyridyl-Nitrogen in the Structural Chemistry of Pyridyl-Substituted Dithiocarbamate Ligands

Crystals ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 286
Author(s):  
Edward R.T. Tiekink
Keyword(s):  
Transition Metal ◽  
Main Group ◽  
Group Element ◽  
Systematic Research ◽  
Pyridyl Nitrogen ◽  
General Observation ◽  
Supramolecular Architectures ◽  
Main Group Element ◽  
Metal Dithiocarbamates

A search of the Cambridge Structural Database was conducted for pyridyl-substituted dithiocarbamate ligands. This entailed molecules containing both an NCS2− residue and pyridyl group(s), in order to study their complexation behavior in their transition metal and main group element crystals, i.e., d- and p-block elements. In all, 73 different structures were identified with 30 distinct dithiocarbamate ligands. As a general observation, the structures of the transition metal dithiocarbamates resembled those of their non-pyridyl derivatives, there being no role for the pyridyl-nitrogen atom in coordination. While the same is true for many main group element dithiocarbamates, a far greater role for coordination of the pyridyl-nitrogen atoms was evident, in particular, for the heavier elements. The participation of pyridyl-nitrogen in coordination often leads to the formation of dimeric aggregates but also one-dimensional chains and two-dimensional arrays. Capricious behaviour in closely related species that adopted very different architectures is noted. Sometimes different molecules comprising the asymmetric-unit of a crystal behave differently. The foregoing suggests this to be an area in early development and is a fertile avenue for systematic research for probing further crystallization outcomes and for the rational generation of supramolecular architectures.

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