Clemens Bruhn
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View article: Group 10 and Group 11 Metal Complexes of a Thermally Stable N‐Heterocyclic Carbene with a 1,1′‐Ferrocenylene Backbone
Group 10 and Group 11 Metal Complexes of a Thermally Stable N‐Heterocyclic Carbene with a 1,1′‐Ferrocenylene Backbone Open
The reaction of the stable ferrocene‐based N‐heterocyclic carbene (NHC) fc[N(CH 2 Mes)] 2 C ( A ; fc = 1,1 ′ ‐ferrocenylene, Mes = mesityl) with CuX (1 equivalent; X = Cl, Br, I, Mes) afforded [CuX( A )]. [AgCl( A )] is synthesized analogo…
View article: Planar‐Chiral 1,1′‐Diiminoferrocenes [Fe{η<sup>5</sup>‐C<sub>5</sub>H<sub>3</sub>‐1‐(N=CHPh)‐2‐(C≡CAr)}{η<sup>5</sup>‐C<sub>5</sub>H<sub>4</sub>(N=CHPh)}] Containing a Bulky Ethynyl Substituent Adjacent to One of the Imino Groups
Planar‐Chiral 1,1′‐Diiminoferrocenes [Fe{η<sup>5</sup>‐C<sub>5</sub>H<sub>3</sub>‐1‐(N=CHPh)‐2‐(C≡CAr)}{η<sup>5</sup>‐C<sub>5</sub>H<sub>4</sub>(N=CHPh)}] Containing a Bulky Ethynyl Substituent Adjacent to One of the Imino Groups Open
The planar‐chiral stannylated diaminoferrocene [Fe{η 5 ‐C 5 H 3 ‐1‐(Sn n Bu 3 )‐2‐(NH 2 )}{η 5 ‐C 5 H 4 (NH 2 )}] ( A ) and its diimine derivative [Fe{η 5 ‐C 5 H 3 ‐1‐(Sn n Bu 3 )‐2‐(N=CHPh)}{η 5 ‐C 5 H 4 (N=CHPh)}] ( B ) gave unsatisfacto…
View article: Triaminoalkenes Derived from Cyclic (Alkyl)(amino)carbenes with a 1,1′‐Ferrocenylene Backbone and <i>N</i>‐Heterocyclic Carbenes: fcCAAC–NHC Heterodimers
Triaminoalkenes Derived from Cyclic (Alkyl)(amino)carbenes with a 1,1′‐Ferrocenylene Backbone and <i>N</i>‐Heterocyclic Carbenes: fcCAAC–NHC Heterodimers Open
The study addresses triaminoalkenes derived from [3]ferrocenophane‐type cyclic (alkyl)(amino)carbenes (fcCAACs) fc(CPh 2 CNR) (fc = 1,1′‐ferrocenylene) and N ‐heterocyclic carbenes (NHCs). Stable target compounds are obtained in good yie…
View article: Adaptive Coordination Behavior of Bisphosphanylphosphanido‐Ligands Toward Group 2, 11 and 12 Metal Ions
Adaptive Coordination Behavior of Bisphosphanylphosphanido‐Ligands Toward Group 2, 11 and 12 Metal Ions Open
A series of alkaline earth metal complexes (Mg−Ba) with the anionic ferrocenylene‐bridged bisphosphanylphosphanide ligand [Fe(C 5 H 4 PC 4 H 9 ) 2 P] − has been prepared by metalation of the corresponding bisphosphanylhydrophosphane (Fe(C …
View article: Carborane‐Decorated Siloles with Highly Efficient Solid‐State Emissions – What Drives the Photophysical Properties?
Carborane‐Decorated Siloles with Highly Efficient Solid‐State Emissions – What Drives the Photophysical Properties? Open
New hybrids were synthesised by linking carboranes and siloles, both of which are known as aggregation‐induced emission active units. Although most of the newly synthesised systems do not display notable quantum yield either in solution or…
View article: β-Carboxyphospholes <i>via</i> carboxylative desilylation: luminophores with a versatile connectivity attached
β-Carboxyphospholes <i>via</i> carboxylative desilylation: luminophores with a versatile connectivity attached Open
Attachment of a carboxylic group, one of the most flexible functionalities in chemistry, to luminescent phospholes has been accomplished, paving the way to facile derivatization, including bioconjugation.
View article: The “pogo stick” complex [FeCp*{N(SiMe<sub>3</sub>)<sub>2</sub>}]: spin state properties, adduct formation with Lewis bases, and reactivity towards weakly Brønsted acidic protonated NHCs
The “pogo stick” complex [FeCp*{N(SiMe<sub>3</sub>)<sub>2</sub>}]: spin state properties, adduct formation with Lewis bases, and reactivity towards weakly Brønsted acidic protonated NHCs Open
The Fe II complex [FeCp*{N(SiMe 3 ) 2 }] reacts readily with formamidinium cations ( i.e. protonated NHCs) in the presence of halide anions via [FeCp*X{N(SiMe 3 ) 2 }] − (X = Cl, Br, I) to furnish [FeCp*X(NHC)] and HN(SiMe 3 ) 2 , but is i…
View article: P<sup>+</sup> addition and transfer involving a tetraphosphenium ion
P<sup>+</sup> addition and transfer involving a tetraphosphenium ion Open
Formal addition of “P + ” to an electrophilic bisphosphanylphosphenium ion, results in the formation of a dicationic tetraphosphenium ion featuring a remarkably long P–P bond between trivalent P-atoms and super Lewis acidic character.
View article: A Strongly Ambiphilic Ferrocene‐Based Cyclic (Alkyl)(amino)carbene – Specific Decomposition to an Enamine by a 1,2‐Phenyl Shift
A Strongly Ambiphilic Ferrocene‐Based Cyclic (Alkyl)(amino)carbene – Specific Decomposition to an Enamine by a 1,2‐Phenyl Shift Open
The recently described crystalline cyclic (alkyl)(amino)carbene with a 1,1’‐ferrocenylene (fc) backbone fc(CPh 2 −C−NMes) ( A , Mes=mesityl) is highly reactive due to its particularly pronounced ambiphilicity and is thermally not stable in…
View article: Exploring the Stability of Primary Phosphine Oxides: Correlation with Primary Phosphine′s Air‐Stability?
Exploring the Stability of Primary Phosphine Oxides: Correlation with Primary Phosphine′s Air‐Stability? Open
To better understand the stability of isolable primary phosphine oxides, new members of this family were synthesized through the oxidation of the corresponding phosphines. Specifically, the previously reported air‐stable primary phosphines…
View article: Synthesis and Characterization of NHC Stabilized Bis(phenylsulfanyl)stannylene
Synthesis and Characterization of NHC Stabilized Bis(phenylsulfanyl)stannylene Open
Reaction of two equivalents of ((CH 3 ) 3 Si) 2 C(C 6 H 5 )SLi ⋅ 3THF with SnCl 2 ⋅IDipp(IDipp=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene) led to fragmentation of the organolithium component and gave IDipp⋅Sn(SPh) 2 , compound 3 . Th…
View article: An N‐Heterocyclic Germylene and Stannylene with a 1,1’‐Ferrocenylene Backbone and Dimesitylboryl <i>N</i>‐Substituents
An N‐Heterocyclic Germylene and Stannylene with a 1,1’‐Ferrocenylene Backbone and Dimesitylboryl <i>N</i>‐Substituents Open
The diaminoferrocene derivative fc[NH(BMes 2 )] 2 ( 1 H 2 ; fc=1,1’‐ferrocenylene, Mes=mesityl) was prepared from fc(NH 2 ) 2 and Mes 2 BCl and used for the preparation of the N‐heterocyclic tetrylenes fc{[N(BMes 2 )] 2 E} ( 1 E, E=Ge, Sn)…
View article: Application of Primary Phosphine Oxides in Domino‐Phospha‐Aldol Reactions of Diketones
Application of Primary Phosphine Oxides in Domino‐Phospha‐Aldol Reactions of Diketones Open
An approach for the preparation and stabilization of primary phosphine oxides is presented complementing previous methods of in situ generation. Specifically, RP(O)H 2 where R=benzyl (Bn), cyclohexyl (Cy), 2‐naphthyl (2‐Naph), phenyl (Ph),…
View article: Ferrocene‐Based <i>N</i>‐Heterocyclic Silylenes: Monomeric Silanechalcogenones, Silanimines, Silirenes, and Insertion Products with P<sub>4</sub>
Ferrocene‐Based <i>N</i>‐Heterocyclic Silylenes: Monomeric Silanechalcogenones, Silanimines, Silirenes, and Insertion Products with P<sub>4</sub> Open
The stable ferrocene‐based N ‐heterocyclic silylenes fc[(N{B}) 2 Si] ( A ; fc=1,1’‐ferrocenylene, {B}=(HCNDipp) 2 B, Dipp=2,6‐diisopropylphenyl) and fc[(NDipp) 2 Si] ( B ) are compared in a study focussing on their reactivity towards a ran…
View article: Phospholanes via Twofold C‐H‐Addition to Phospholes
Phospholanes via Twofold C‐H‐Addition to Phospholes Open
A synthetic route towards phospholanes via twofold C−H‐addition of a DMSO molecule to β‐H substituted phospholes is described. The resulting fused phospholane oxothiolane system in case of symmetric α‐substitution possesses four stereogeni…
View article: Synthesis, structure, and stability of a set of C-stereogenic heteroditopic P, S ligands
Synthesis, structure, and stability of a set of C-stereogenic heteroditopic P, S ligands Open
This study focuses on synthesis and investigation of coordination modes of phosphorus and sulfur-containing C-stereogenic compounds, prepared from thioanisole. Isolation of the C-stereogenic organolithium compound [RR'CHLi·2THF]2 (R = C6H5…
View article: Controlled Ring Opening of a Tetracyclic Tetraphosphane with Twofold Metallocene Bridging
Controlled Ring Opening of a Tetracyclic Tetraphosphane with Twofold Metallocene Bridging Open
A direct route to a doubly ferrocene bridged tetracyclic tetraphosphane 1 was developed via reductive coupling of Fe(CpPCl 2 ) 2 ( 2 a ), where a chlorine terminated linear P 4 ‐compound 3 could be identified as an intermediate. Selective …
View article: Tuning the Sterics: Rh-Catalyzed Hydroformylation Reactions with Ferrocene Based Diphosphorus Ligands
Tuning the Sterics: Rh-Catalyzed Hydroformylation Reactions with Ferrocene Based Diphosphorus Ligands Open
View article: Synthesis, Structure, and Stability of a Set of C-Stereogenic Heteroditopic P, S Ligands
Synthesis, Structure, and Stability of a Set of C-Stereogenic Heteroditopic P, S Ligands Open
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View article: Gradual Coordination and Reversible P–P Bond Activation of a P<sub>3</sub>‐Unit with Transition Metal Carbonyls
Gradual Coordination and Reversible P–P Bond Activation of a P<sub>3</sub>‐Unit with Transition Metal Carbonyls Open
Coordination of a stereochemically defined P 3 ‐chain to a series of transition metal carbonyls [M(CO) x ] z− (M = Mn (x = 5, z = 1), Fe (x = 4, z = 2) or Co (x = 4, z = 1)) is explored using a [3]ferrocenophane scaffold. A gradual transit…
View article: At the limits of bisphosphonio‐substituted stannylenes
At the limits of bisphosphonio‐substituted stannylenes Open
Donor stabilization of Sn(II) and Pb(II) halides with 1,1’‐ferrocenylene bridged bisphosphanes has been explored for Fe(C 5 H 4 P(C 6 H 5 ) 2 ) 2 (dppf), and Fe(C 5 H 4 PH(C 4 H 9 )) 2 . These bisphosphanes are reacted with SnBr 2 and PbCl…
View article: Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(η5-Cp*)X2]− (X = Cl − I)
Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(η5-Cp*)X2]− (X = Cl − I) Open
Half-sandwich iron(II) dihalido complexes of the type [Fe(η5-Cp’)X2]− (Cp’ = C5H5 or substituted cyclopentadienyl) which are thermally stable at room temperature are extremely scarce, being limited to congeners containing the bulky C5H2-1,…
View article: Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(5-Cp*)X2] (X = Cl – I)
Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(5-Cp*)X2] (X = Cl – I) Open
Stable half-sandwich iron(II) dihalido complexes of the type [Fe(5-Cp’)X2] are extremely scarce, being limited to congeners containing the bulky C5H2-1,2,4-tBu3 ligand. We have extended this to homologues [Fe(5-Cp*)X2] (X = Cl – I) contain…
View article: CCDC 2289083: Experimental Crystal Structure Determination
CCDC 2289083: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: CCDC 2289084: Experimental Crystal Structure Determination
CCDC 2289084: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: CCDC 2289085: Experimental Crystal Structure Determination
CCDC 2289085: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: CCDC 2289081: Experimental Crystal Structure Determination
CCDC 2289081: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: CCDC 2259658: Experimental Crystal Structure Determination
CCDC 2259658: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: A General Strategy for Increasing the Air Stability of Phosphines Including Primary Phosphines
A General Strategy for Increasing the Air Stability of Phosphines Including Primary Phosphines Open
A general approach for increasing the air‐stability of various primary phosphines in the absence of kinetic stabilization is presented that contrasts with previous interpretations, which were limited to specific phosphines. This contributi…
View article: Reduction Behavior of Anisyl‐substituted P‐Ferrocenyl Phospholes
Reduction Behavior of Anisyl‐substituted P‐Ferrocenyl Phospholes Open
P‐Ferrocenylphospholes with differing substituents in α‐position have been synthesized and their identity and purity was confirmed using multinuclear NMR spectroscopy, MS, elemental analysis and single crystal X‐ray diffraction. Furthermor…