20 research outputs found
Regioselective functionalization of tetrabromophenanthroline-ruthenium complexes
Get PDFStructural, photophysical and -chemical characterisation and reactivity of a novel polypyridyl
ruthenium complex based on 3,5,6,8-tetra-bromophenanthroline are discussed.
Signal storage at a molecular level is great challenge for chemistry.1 The possibility of
connecting different functionalities selectively to one ligand of a metal complex may open the
route towards higher integrated molecular units capable of processing various external stimuli
in a predesignated order. The implementation of this concept demands ligands with a
multitude of potential connecting groups which can selectively be transformed.2 3-bromo- and
3,8-dibromophenanthrolines have proved useful for the preparation of mononuclear3 and
multiheteronuclear complexes.4 These systems have found applications ranging from DNA
photoprobes5 to metalloligands in catalysis.6 A very useful feature of this
bromophenanthroline ruthenium complexes is their susceptibility towards nucleophilic
aromatic substitution which is very well established
Reactive Intermediates of the Catalytic Carbomagnesation Reaction: Isolation and Structures of [Cp 2
No full textReactivity Studies of [(thf)<sub>2</sub>Mg{μ-C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>C(CH<sub>3</sub>)<sub>2</sub>}]<sub>2</sub>: Scrambling Reactions and Diverse Reactions with Dichlorophenylphosphane
No full textIn
THF solution [{(thf)<sub>2</sub>Mg{μ-C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>(CH<sub>3</sub>)<sub>2</sub>C}}<sub>2</sub>] (<b>1</b>) exchanges the alkanediide ligand with [{(thf)<sub>2</sub>Mg{μ-CH<sub>2</sub>)<sub>5</sub>}}<sub>2</sub>] in an
equilibrium leading to the formation of [{(thf)<sub>2</sub>Mg}<sub>2</sub>{μ-C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>C(CH<sub>3</sub>)<sub>2</sub>}{μ-(CH<sub>2</sub>)<sub>5</sub>}] (<b>2</b>). Depending on the crystallization temperature,
homoleptic <b>1</b> or heteroleptic <b>2</b> crystallizes
from THF solutions, verifying a temperature-dependent Schlenk equilibrium.
Irradiation of a solution of <b>1</b> in [D<sub>8</sub>]THF
with UV light yields magnesium hydride and alkene via a β-hydride
elimination reaction. In a metathetical approach dichlorophenylphosphane reacts with <b>1</b> in THF to give the intermediate “PhP(Cl){C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>(CH<sub>3</sub>)<sub>2</sub>CMgCl” (<b>3-MgCl</b>), which forms three subsequent
products. In order to ease handling and characterization of these
compounds, hydrolysis and oxidation with sulfur has been performed.
This product mixture was separated by column chromatography, yielding
the chlorophosphane sulfide [Ph(S)P(Cl){C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>(CH<sub>3</sub>)<sub>2</sub>CH)}] (<b>3-S</b>), the cyclic phosphane sulfide [Ph(S)P{C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>(CH<sub>3</sub>)<sub>2</sub>C)}] (<b>4-S</b>), and the cyclic 1,1-diphosphane disulfide
[{(Ph(S)P}<sub>2</sub>{μ-C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>(CH<sub>3</sub>)<sub>2</sub>C}] (<b>6-S<sub>2</sub></b>). Furthermore, traces of the acyclic 1,1-diphosphane
disulfides [{PhP(S)(C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>CH(CH<sub>3</sub>)<sub>2</sub>)}{PhP(S)(C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>C(CH<sub>3</sub>)(CH<sub>2</sub>)}] (<b>8-S<sub>2</sub></b>) and <i>meso</i>-[{Ph(S)P(C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>(CH<sub>3</sub>)<sub>2</sub>CH)}<sub>2</sub>] (<b>7-S<sub>2</sub></b>) have also
been isolated. Compounds <b>6</b>–<b>8</b> represent
the phosphorus-containing products of indirect Grignard reductions
Reactivity Studies of [(thf)<sub>2</sub>Mg{μ-C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>C(CH<sub>3</sub>)<sub>2</sub>}]<sub>2</sub>: Scrambling Reactions and Diverse Reactions with Dichlorophenylphosphane
No full textIn
THF solution [{(thf)<sub>2</sub>Mg{μ-C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>(CH<sub>3</sub>)<sub>2</sub>C}}<sub>2</sub>] (<b>1</b>) exchanges the alkanediide ligand with [{(thf)<sub>2</sub>Mg{μ-CH<sub>2</sub>)<sub>5</sub>}}<sub>2</sub>] in an
equilibrium leading to the formation of [{(thf)<sub>2</sub>Mg}<sub>2</sub>{μ-C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>C(CH<sub>3</sub>)<sub>2</sub>}{μ-(CH<sub>2</sub>)<sub>5</sub>}] (<b>2</b>). Depending on the crystallization temperature,
homoleptic <b>1</b> or heteroleptic <b>2</b> crystallizes
from THF solutions, verifying a temperature-dependent Schlenk equilibrium.
Irradiation of a solution of <b>1</b> in [D<sub>8</sub>]THF
with UV light yields magnesium hydride and alkene via a β-hydride
elimination reaction. In a metathetical approach dichlorophenylphosphane reacts with <b>1</b> in THF to give the intermediate “PhP(Cl){C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>(CH<sub>3</sub>)<sub>2</sub>CMgCl” (<b>3-MgCl</b>), which forms three subsequent
products. In order to ease handling and characterization of these
compounds, hydrolysis and oxidation with sulfur has been performed.
This product mixture was separated by column chromatography, yielding
the chlorophosphane sulfide [Ph(S)P(Cl){C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>(CH<sub>3</sub>)<sub>2</sub>CH)}] (<b>3-S</b>), the cyclic phosphane sulfide [Ph(S)P{C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>(CH<sub>3</sub>)<sub>2</sub>C)}] (<b>4-S</b>), and the cyclic 1,1-diphosphane disulfide
[{(Ph(S)P}<sub>2</sub>{μ-C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>(CH<sub>3</sub>)<sub>2</sub>C}] (<b>6-S<sub>2</sub></b>). Furthermore, traces of the acyclic 1,1-diphosphane
disulfides [{PhP(S)(C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>CH(CH<sub>3</sub>)<sub>2</sub>)}{PhP(S)(C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>C(CH<sub>3</sub>)(CH<sub>2</sub>)}] (<b>8-S<sub>2</sub></b>) and <i>meso</i>-[{Ph(S)P(C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>(CH<sub>3</sub>)<sub>2</sub>CH)}<sub>2</sub>] (<b>7-S<sub>2</sub></b>) have also
been isolated. Compounds <b>6</b>–<b>8</b> represent
the phosphorus-containing products of indirect Grignard reductions
Reaction of Alkenylzirconocenes with Dialkylzirconocenes: Unexpected Formation of Bimetallic (μ-Alkynyl)zirconocene Complexes
No full textMetal Complexes with 2,3-Bis(diphenylphosphino)-1,4-diazadiene Ligands: Synthesis, Structures, and an Intramolecular Metal-Mediated [4 + 2] Cycloaddition Employing a Benzene Ring as a Dienophile
No full textSynthesis, Crystal Structures, and Solution Behavior of Organomagnesium Derivatives of Alkane-1,4-diide as Well as -1,5-diide
No full textThe organomagnesium complexes [(thf)<sub>2</sub>Mg(μ-C<sub>5</sub>H<sub>10</sub>)]<sub>2</sub> (<b>1</b>), [(thf)<sub>2</sub>Mg(μ-C<sub>4</sub>H<sub>8</sub>)]<sub>∞</sub> (<b>2</b>), and [(thf)<sub>2</sub>Mg(μ-(C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>C(CH<sub>3</sub>)<sub>2</sub>)]<sub>2</sub> (<b>3</b>) were prepared via direct synthesis
from magnesium turnings and appropriate dichloroalkanes in tetrahydrofuran
(THF). The aggregation degree in the solid state depends on the nature
of the alkanediide. The THF solution of <b>3</b> shows a temperature-dependent
equilibrium. The reactions of MgCl<sub>2</sub>(thf)<sub>1.5</sub> with
1,4-dilithiobutane yield the lithium magnesiates [Li(thf)<sub>4</sub>]<sub>2</sub>[Mg<sub>3</sub>(C<sub>4</sub>H<sub>8</sub>)<sub>4</sub>] (<b>4</b>) and [{(tmeda)Li}<sub>2</sub>Mg(C<sub>4</sub>H<sub>8</sub>)<sub>2</sub>] (<b>5</b>) depending on the applied stoichiometry.
The addition reaction of Ph<sub>2</sub>Mg(diox) (1,4-dioxane = diox)
with 1,4-dilithiobutane leads to the formation of the heteroleptic
magnesiate [{(tmeda)Li}<sub>2</sub>MgPh<sub>2</sub>(C<sub>4</sub>H<sub>8</sub>)] (<b>6</b>), which shows in THF solution a ligand
exchange (Schlenk-type) equilibrium with the homoleptic derivatives
[{(thf)<sub>2</sub>Li}<sub>2</sub>Mg(C<sub>4</sub>H<sub>8</sub>)<sub>2</sub>] and [{(thf)<sub>2</sub>Li}<sub>2</sub>MgPh<sub>4</sub>]
Synthesis, Crystal Structures, and Solution Behavior of Organomagnesium Derivatives of Alkane-1,4-diide as Well as -1,5-diide
No full textThe organomagnesium complexes [(thf)<sub>2</sub>Mg(μ-C<sub>5</sub>H<sub>10</sub>)]<sub>2</sub> (<b>1</b>), [(thf)<sub>2</sub>Mg(μ-C<sub>4</sub>H<sub>8</sub>)]<sub>∞</sub> (<b>2</b>), and [(thf)<sub>2</sub>Mg(μ-(C(CH<sub>3</sub>)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>C(CH<sub>3</sub>)<sub>2</sub>)]<sub>2</sub> (<b>3</b>) were prepared via direct synthesis
from magnesium turnings and appropriate dichloroalkanes in tetrahydrofuran
(THF). The aggregation degree in the solid state depends on the nature
of the alkanediide. The THF solution of <b>3</b> shows a temperature-dependent
equilibrium. The reactions of MgCl<sub>2</sub>(thf)<sub>1.5</sub> with
1,4-dilithiobutane yield the lithium magnesiates [Li(thf)<sub>4</sub>]<sub>2</sub>[Mg<sub>3</sub>(C<sub>4</sub>H<sub>8</sub>)<sub>4</sub>] (<b>4</b>) and [{(tmeda)Li}<sub>2</sub>Mg(C<sub>4</sub>H<sub>8</sub>)<sub>2</sub>] (<b>5</b>) depending on the applied stoichiometry.
The addition reaction of Ph<sub>2</sub>Mg(diox) (1,4-dioxane = diox)
with 1,4-dilithiobutane leads to the formation of the heteroleptic
magnesiate [{(tmeda)Li}<sub>2</sub>MgPh<sub>2</sub>(C<sub>4</sub>H<sub>8</sub>)] (<b>6</b>), which shows in THF solution a ligand
exchange (Schlenk-type) equilibrium with the homoleptic derivatives
[{(thf)<sub>2</sub>Li}<sub>2</sub>Mg(C<sub>4</sub>H<sub>8</sub>)<sub>2</sub>] and [{(thf)<sub>2</sub>Li}<sub>2</sub>MgPh<sub>4</sub>]
Intermolecular Coupling Reaction of Alkynes with Vinyl Bromide with Selective Skeletal Rearrangement
No full text
