Transition‐Metal‐Like Catalysis with a Main‐Group Element: Bismuth‐Catalyzed C−F Coupling of Aryl Boronic Esters

2020 ◽  
Vol 59 (22) ◽  
pp. 8328-8330 ◽  
Author(s):  
Daniel Janssen‐Müller ◽  
Martin Oestreich
Keyword(s):  
Transition Metal ◽  
Main Group ◽  
Group Element ◽  
Main Group Element ◽  
Boronic Esters

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.

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

scholarly journals A Structural Survey of Poly-Functional Dithiocarbamate Ligands and the Aggregation Patterns They Sustain

Inorganics ◽  
2021 ◽  
Vol 9 (1) ◽  
pp. 7
Author(s):  
See Mun Lee ◽  
Edward R. T. Tiekink
Keyword(s):  
Transition Metal ◽  
Crystal Structures ◽  
Heavy Element ◽  
Three Dimensional ◽  
Main Group ◽  
Group Element ◽  
Main Group Element

An overview is presented of the crystal structures of transition metal, main group element, and lanthanide compounds containing poly-functional dithiocarbamate ligands, namely species containing two or more connected NCS2− residues. In all, there are 40 different ligands of this type that have been characterised crystallographically in their heavy-element compounds with up to six NCS2− residues; all are bridging. In most cases, the resulting aggregates are zero-dimensional, often di-nuclear, but aggregates of up to 36 metal (gold) atoms are noted. There are smaller numbers of one-, two-, and three-dimensional architectures sustained by poly-functional dithiocarbamate ligands in their respective crystals. The survey highlights the opportunities afforded by this generally under-studied class of ligand.

1.2-Verzweigte Carbosiloxan-Dendrimere mit Hauptgruppenelementund Übergangsmetall-modifizierten Oberflächen / 1.2-Branched Carbosiloxane-Dendrimers with Main-Group Element and Transition-Metal Modified Surfaces

1999 ◽  
Vol 54 (6) ◽  
pp. 751-756 ◽  
Author(s):  
Karin Brüning ◽  
Bettina Lühmann ◽  
Heinrich Lang
Keyword(s):  
Transition Metal ◽  
Second Generation ◽  
Spectroscopic Studies ◽  
Main Group ◽  
Group Element ◽  
H Nmr ◽  
Main Group Element ◽  
Elemental Analyses ◽  
Modified Surfaces ◽  
First And Second Generation

The preparation of the first and second generation carbosiloxane dendrimers Si[OCH2- CH2CH2 SiMe(OCH2C=CH)2]4 (3) and Si{OCH2H2CH2SiMe[OCH2CH2CH2SiMe(OCH2 - C=CH)2]2}4 (5) by the reaction o f Si(OCH2CH2CH2SiMeCl2)4 (1) or Si[OCH2CH2CH2SiMe- (OCH2CH2CH2SiMeCl2)2]4 (4) with HOCH2C =CH (2) in the presence o f NEt3 is described. Dendrimers 3 and 5 contain propargyloxy units as terminal groups, which can be transferred to Co2((CO)8 (6) to give the hexacarbonyldicobalt functionalized dendritic molecules Si{OCH2CH2CH2[(η-OCH2C=CH)CO2(CO)6]2}4 (7) and Si{OCH2CH2CH2SiMe-(OCH2CH2CH2SiMe[(η-OCH2C=CH)CO2(CO)6]2)2}4 (8). All compounds were characterized by elemental analyses, spectroscopic studies (IR,1H-, 13C{1H }-, 29Si{1H} NMR) as well as GPC investigations

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>

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