The Charge Transfer Approach to Heavier Main‐Group Element Radicals in Transition‐Metal Complexes

2017 ◽  
Vol 129 (41) ◽  
pp. 12915-12919 ◽  
Author(s):  
Gengwen Tan ◽  
Jing Li ◽  
Li Zhang ◽  
Chao Chen ◽  
Yue Zhao ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Main Group ◽  
Group Element ◽  
Main Group Element

The Charge Transfer Approach to Heavier Main‐Group Element Radicals in Transition‐Metal Complexes

2017 ◽  
Vol 56 (41) ◽  
pp. 12741-12745 ◽  
Author(s):  
Gengwen Tan ◽  
Jing Li ◽  
Li Zhang ◽  
Chao Chen ◽  
Yue Zhao ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Main Group ◽  
Group Element ◽  
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.

scholarly journals Frustration across the periodic table: heterolytic cleavage of dihydrogen by metal complexes

2017 ◽  
Vol 375 (2101) ◽  
pp. 20170002 ◽  
Author(s):  
R. Morris Bullock ◽  
Geoffrey M. Chambers
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Molecular Complexes ◽  
Main Group ◽  
Lewis Base ◽  
Metal Compounds ◽  
Metal Catalysis ◽  
Heterolytic Cleavage ◽  
Lewis Pairs

This perspective examines frustrated Lewis pairs (FLPs) in the context of heterolytic cleavage of H 2 by transition metal complexes, with an emphasis on molecular complexes bearing an intramolecular Lewis base. FLPs have traditionally been associated with main group compounds, yet many reactions of transition metal complexes support a broader classification of FLPs that includes certain types of transition metal complexes with reactivity resembling main group-based FLPs. This article surveys transition metal complexes that heterolytically cleave H 2 , which vary in the degree that the Lewis pairs within these systems interact. Many of the examples include complexes bearing a pendant amine functioning as the base with the metal functioning as the hydride acceptor. Consideration of transition metal compounds in the context of FLPs can inspire new innovations and improvements in transition metal catalysis. This article is part of the themed issue ‘Frustrated Lewis pair chemistry’.

New main-group and early transition-metal complexes of mono-pendant arm triazacyclononane ligands

2001 ◽  
pp. 170-180 ◽  
Author(s):  
Sergei Y. Bylikin ◽  
David A. Robson ◽  
Nigel A. H. Male ◽  
Leigh H. Rees ◽  
Philip Mountford ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Main Group ◽  
Early Transition Metal ◽  
Pendant Arm ◽  
Early Transition

Silicon-Containing Main Group - Transition Metal Complexes

2008 ◽  
pp. 199-200
Author(s):  
Martin Strampfer ◽  
Michael Knorr ◽  
Pierre Braunstein
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Main Group

Molecular and electronic structure in the metal-to-ligand charge-transfer excited states of d6 transition-metal complexes in solution

1984 ◽  
Vol 106 (12) ◽  
pp. 3492-3500 ◽  
Author(s):  
Jonathan V. Caspar ◽  
T. David Westmoreland ◽  
George H. Allen ◽  
Paul G. Bradley ◽  
Thomas J. Meyer ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Charge Transfer ◽  
Transition Metal ◽  
Metal Complexes ◽  
Excited States ◽  
Transition Metal Complexes ◽  
Ligand Charge Transfer ◽  
Molecular And Electronic Structure
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