Alexander Hinz

Alexander Hinz
Karlsruhe Institute of Technology | KIT · Institute of Inorganic Chemistry

Dr

About

120
Publications
4,598
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1,501
Citations
Additional affiliations
April 2018 - present
Karlsruhe Institute of Technology
Position
  • Habilitand
October 2015 - present
University of Oxford
Position
  • PDRA
October 2012 - September 2015
University of Rostock
Position
  • PhD Student

Publications

Publications (120)
Article
Full-text available
Mono‐coordinated silicon(II) cations are predicted to be reactive ambiphiles, combining the typically high Lewis acidity of silicon cations with nucleophilicity due to the presence of an electron pair at the same atomic centre. Here, a carbazole‐derived scaffold was used to isolate salts with a mono‐coordinated silicon(II) cation, [RSi]+ (R = bulky...
Article
Full-text available
The synthesis and isolation of the 2-arsaethynolate anion, AsCO(-) , and its subsequent reactivity towards heteroallenes is reported. Reactions with ketenes and carbodiimides afford four-membered anionic heterocycles in formal [2+2] cycloaddition reactions. By contrast, reaction with an isocyanate yielded a 1,4,2-diazaarsolidine-3,5-dionide anion a...
Article
Full-text available
We describe the isolation and spectroscopic characterization of the heavier phosphorus-containing analogue of isocyanic acid (HPCO), and its isotopologue (DPCO). This fundamental small molecule, which has been postulated to exist in interstellar space, has thus far only been observed at low gas phase concentrations or in inert gas matrices. In this...
Article
In this contribution, the synthesis and properties of nine novel 3d metal complexes are reported. As supporting ligand scaffold, the bulky 1,8‐bis(3,5‐ditertbutylphenyl)‐3,6‐ditertbutylcarbazole (R) was employed. After deprotonation and salt metathesis reactions, a series of four complexes, the dimeric [RMn(THF)(µ‐Cl)] 2 ( 1a ), [RFe(THF)(µ‐Cl)] 2...
Article
The reaction of the dilithium salt of the enantiopure ( S )‐BINOL (1,1’‐bi‐2‐naphthol) with two equivalents of the amidinate‐stabilized chlorosilylene L Ph SiCl (L Ph = PhC(N t Bu) 2 ) led to the formation of the first example of a chiral cyclic silene species comprising a ( S )‐BINOL ligand. The reactivity of the Si=C bond was investigated by reac...
Article
The coordination chemistry of silylenes is known for a vast number of elements of all blocks of the periodic table. However, only a handful of examples of silylene complexes have been reported for heavy alkaline‐earth elements, which is mainly attributed to the “hard‐soft” mismatch between the “hard” metal center and the “soft” silicon donor. Herei...
Article
An air- and moisture-stable helical radical with seven six- and five-membered rings arranged alternately was synthesized by cyclizations in a suitably ortho,ortho'-substituted terphenyl and re-establishment of its conjugation. Mesityl groups at the five-membered rings prevent radical reactions. This cyclopenta-fused polyaromatic hydrocarbon (CP-PAH...
Article
The synthesis and characterisation of rare-earth metal complexes with redox-active formazanate ligands are described. Deprotonation of the neutral formazan ligand L1H (L1 = PhNNC(Ph)NNPh) with [Ln{N(SiMe3)2}3] (Ln = Y, Sm, Dy) resulted in homoleptic tris(formazanate) complexes with the general formula [(L1)3Ln] (Ln = Y (1), Sm (2), Dy (3)), in whic...
Article
The synthesis and properties of silanes bearing a bulky carbazolyl substituent are described. Metathesis routes with different reagents under different conditions are required to obtain the compounds of the general formula RSi(X)2H and RSi(X)2All (X=Cl, N3, NCO, NCS, NH2, All=CH2CHCH2). The silanes were studied by XRD, NMR and IR spectroscopy and a...
Article
Four aryl cobalt and iron complexes, [(F4C5N)Co(Cl)(PMe3)3] (1), [(F4C5N)Fe(PMe3)4] (2), [(F5C6)Co(Cl)(PMe3)3] (3) and [(F5C6)Fe(Cl)(PMe3)3] (4) were synthesized from the reactions of 3-chloro-2,4,5,6-tetrafluoro-pyridine and chloropentafluorobenzene with Co(PMe3)4 and Fe(PMe3)4 respectively. Under...
Article
Competition for the lone pair: Our paper describes efforts to access cationic α‐silylated (and α‐germylated) phosphorus ylides of the general formula [R3PC(R)SiR2]+. One inherent feature of these molecules is that the silyl and phosphonyl entities compete for the lone pair of electrons. The ambivalent nature of the possible resonance structures is...
Article
We report details of our attempts to reduce the bulky carbazolyl diiodoalane [R-AlI2]. The reducing agents employed include KC8, Cp*2Co and the Mg(I) compound [(MesBDI)Mg]2. The use of KC8 allowed the spectroscopic observation of the alanediyl [R-Al]. With Cp*2Co as the reducing agent, the alanediyl [R-Al] was obtained as a crystalline material in...
Article
The synthesis and full characterization of α‐silylated (α‐SiCPs, 1‐7) and α‐germylated (α‐GeCPs) (11‐13) phosphorus ylides bearing one chloride substituent R3PC(R1)E(Cl)R22 (R = Ph; R1 = Me, Et, Ph; R2 = Me, Et, iPr, Mes; E = Si, Ge) is presented. The molecular structures were determined by X‐ray diffraction studies. The title compounds were applie...
Article
Full-text available
In this work we detail our efforts to systematically generate stable dicoordinate Cu(II) complexes. Initial experiments via metathesis reactions of a bulky potassium carbazolide (RK) with copper(II) salts indeed yielded a stable product, RCuOTf ( 1 ). However, subsequent attempts to grasp systematic synthetic access to complexes of the type RCuX (X...
Article
Full-text available
Metalloradicals are key species in synthesis, catalysis, and bioinorganic chemistry. Herein, two iron radical cation complexes ( 3‐E )GaCl 4 [( 3‐E ) •+ = [{(IPr)C(Ph)E} 2 Fe(CO) 3 ] •+ , E = P or As; IPr = C{(NDipp)CH} 2 , Dipp = 2,6‐ i Pr 2 C 6 H 3 ] are reported as crystalline solids. Treatment of the divinyldipnictenes {(IPr)C(Ph)E} 2 ( 1‐E ) w...
Article
Full-text available
Stepwise metalation and metathesis reactions with a bulky aminocarbazole were conducted to prepare derivatives of tetravalent group 14 elements. These were regarded as putatively suitable precursors for the formation of doubly bonded group 14/group 15 molecules such as imino species. Starting from an N‐aminocarbazole, deprotonation with benzyl pota...
Article
Full-text available
Phosphorus centered biradicaloids of the type [P(μ‐NTer)]2 [R = Ter = terphenyl = 2,6‐bis(2,4,6‐trimethylphenyl)phenyl, Hyp = tris(trimethylsilyl)silyl] were treated with covalent (R‐N3) and ionic azides (AgN3 and Hg(N3)2). While the reaction with the ionic azides led exclusively to the formation of diazides, [N3P(μ‐NTer)]2, triaza‐diphospha‐pentad...
Article
Full-text available
Ein einfach koordiniertes Siliziumkation wurde durch Halogenidabstraktion von einem Iodosilylen dargestellt. Es wird gezeigt, dass in der Reaktion mit einem Amin drei Bindungen am Siliziumatom in einer Reaktion gebildet werden können, was mit dem Konzept eines „Supersilylens“ einhergeht. Abstract Einfach koordinierte Silizium(II)‐Kationen werden a...
Article
2-Arsa-1,3-butadienes (L)As(cAACR) (L = PhC=C{(NDipp)CH}2, Dipp = 2,6-iPr2C6H3; cAACR = C{(NDipp)CMe2CH2C(R)}, R = Me2 2a, R = cyclohexyl (Cy) 2b) and the corresponding radical cations [(L)}As-(cAACR)]GaCl4 (R = Me2 3a, Cy 3b) and dications [(L)As(cAACR)]-(GaCl4)2 (R = Me 4a, Cy 4b) featuring a C=C‒As=C π-conjugated framework are reported.
Article
Full-text available
A synthetic strategy for the 2-phospha-1,3-butadiene derivatives [{(IPr)C(Ph)}P(cAACMe)] (3a) and [{(IPr)C(Ph)}P(cAACCy)] (3b) (IPr = C{(NDipp)CH2}2, Dipp = 2,6-iPr2C6H3; cAACMe = C{(NDipp)CMe2CH2CMe2}; cAACCy = C{(NDipp)CMe2CH2C(Cy)}, Cy = cyclohexyl) containing a C=C‒P=C framework has been established. Compounds 3a and 3b have a remarkably small...
Article
Cyanate Homologues Four heavier CN− homologues were studied by negative‐ion photoelectron spectroscopy, photoelectron‐imaging spectroscopy, and quantum‐chemical computations by J. M. Goicoechea, B. Chen, X.‐B. Wang et al. in their Research Article on page 15062 ff.
Article
Cyanat‐Homologe Vier schwere CN−‐Homologe wurden von J. M. Goicoechea, B. Chen, X.‐B. Wang et al. mittels Negativionen‐Photoelektronenspektroskopie, Photoelektronenbildgebung und quantenchemischen Berechnungen in ihrem Forschungsartikel auf S. 15206 untersucht.
Article
Full-text available
The divinyldiarsene radical cations [{(NHC)C(Ph)}As]2­(GaCl4) (NHC = IPr: C{(NDipp)CH}2 3; SIPr: C{(NDipp)CH2}2 4; Dipp = 2,6‐iPr2C6H3) and dications [{(NHC)C(Ph)}As]2(GaCl4)2 (NHC = IPr 5; SIPr 6) are readily accessible as crystalline solids on sequential one‐electron oxidation of the corresponding divinyldiarsenes [{(NHC)C(Ph)}As]2 (NHC = IPr 1;...
Article
Full-text available
Die stufenweise Oxidation von Diarsenen [As2], die N‐heterocyclische Vinyl‐π‐Donorsubstituenten tragen, mit GaCl3 führt zur Bildung von Radikalkationen [As2]+. und Dikationen [As]²⁺ in kristallinen Feststoffen. Experimentelle und theoretische Studien bestätigen die Delokalisierung des ungepaarten Elektrons über das π‐konjugierte CAs2C‐Gerüst. Abst...
Article
Schwergewichte: Vier schwere Homologe des Cyanat‐Anions, ECX⁻ (E=N, P, As; X=O, S, Se), wurden mittels Negativionen‐Photoelektronenspektroskopie, Photoelektronenbildgebung und quantenchemischen Berechnungen untersucht. Die gemessenen Elektronenaffinitäten (EAs) und Spin‐Bahn‐Aufspaltungen erlauben es, die vollständigen EA‐ und Spin‐Bahn‐Matrizen de...
Article
The newly synthesized, phosphorus- and arsenic-containing analogues of the thio- and seleno-cyanate anions, PCSe-, AsCS-, and AsCSe-, as well as the known ion NCSe-, were investigated in the gas phase by negative ion photoelectron spectroscopy (NIPES), velocity-map imaging (VMI) spectroscopy, and quantum chemical computations. The electron affiniti...
Article
The synthesis and charcterization of the crystalline diphosphene radical cations [{(NHC)C(Ph)}P]2(GaCl4) (NHC = IPr = C{(NDipp)CH}2 3, SIPr = C{(NDipp)CH2}2 4; Dipp = 2,6-iPr2C6H3) and dications [{(NHC)C(Ph)}P]2¬(GaCl4)2 (NHC = IPr...
Article
Full-text available
Correction for ‘Increasing steric demand through flexible bulk – primary phosphanes with 2,6-bis(benzhydryl)phenyl backbones’ by Jonas Bresien et al. , Dalton Trans. , 2019, 48 , 3786–3794.
Article
The isolation of rhenium(V) complexes with terminal phosphide and arsenide ligands was achieved upon decarbonylation of rhenium(III) pnictaethynolates. One-electron oxidation of the pnictide complexes yielded Pn-Pn (Pn=P, As) coupling products, which were spectroscopically and crystallographically characterized. Computational bond analysis suggests...
Article
The isolation of rhenium(V) complexes with terminal phosphide and arsenide ligands was achieved upon decarbonylation of rhenium(III) pnictaethynolates. One‐electron oxidation of the pnictide complexes yielded Pn−Pn (Pn=P, As) coupling products, which were spectroscopically and crystallographically characterized. Computational bond analysis suggests...
Article
The synthesis of the N‐aminocarbazole R‐NH2 (2) is reported. Subsequent reaction with bis[bis(trimethylsilyl)amido]tetrylenes E[N(SiMe3)2]2 (E=Ge, Sn, or Pb) allowed the isolation of formal hydrazidotetrylene derivatives, R−N(H)EN(SiMe3)2 (3) that includes the first example of a hydrazidoplumbylene to date. Thermal decomposition of these compounds...
Article
Sterically demanding primary phosphanes of the type RBhp−PH2 (Bhp = 2,6-bis(benzhydryl)-4-R-phenyl; R = Me, tBu) could be prepared in high yields by modification of synthetic protocols of established bulky phosphanes. The Bhp substituents simultaneously exhibit extensive steric expansiveness and high degrees of flexibility compared to other 2,6-sub...
Article
Syntheses of a bulky carbazole‐based substituent, the parent 1,8‐bis(3,5‐di‐tert‐butylphenyl)‐3,6‐di‐tert‐butyl‐carbazole (R−H) and a series of chlorotetrylenes, RECl (E=Ge, Sn, Pb), are described. Detailed analysis of the properties of the carbazole‐based substituent revealed that it features flexible high bulkiness and electronic non‐innocence, w...
Article
A key intermediate in the formation of a bicyclic cage formed between a biradical (LCP)2 (L = carbene) and an unsaturated substrate via a [2+2] cycloaddition reaction has been isolated...
Article
The cover picture shows a (distorted) square planar bromide coordination environment about a silver cation. The application of soluble silver salts for halide abstraction is a common preparative routine in organometallic chemistry. If the oxidation power of Ag+ is restricting, respective thallium salt can be an alternative. The paper of Kleinschmid...
Article
Halide addition and abstraction experiments with the cationic rhenacyclopentatriene [(η⁵‐C5H5){ReC4(SBn)4}Br]BF4 and the side‐on cyclobutadiene complexes [(η⁵‐C5H5)(η⁴‐C4Ph4)ReX2] (X = Br, I), respectively, are described. Reversible interconversion of both coordination modes of the metal bonded C4R4 moiety depending on the presence or absence of th...
Article
The synthesis of a novel heterocubane [RSnE]4 was successful for E = As, while for E = P differing behaviour was observed. Aryl-substituted chlorostannylenes were treated with salts of heavy cyanate homologues PCO– and AsCO–. The reaction with AsCO– salts afforded primarily [TerSnAs]4 (Ter = 2,6-dimesitylphenyl). In contrast, the reaction of TerSnC...
Article
Das erste stabile Aluminium‐Nukleophil wurde von Goicoechea, Aldridge und Mitarbeitern isoliert. Die Aluminyl‐Verbindung zeigt eine sehr hohe Reaktivität sowohl bei Metathesereaktionen als auch bei oxidativen Additionen von Substraten wie Wasserstoff und Benzol, was neue Perspektiven in der Hauptgruppenchemie eröffnet.
Article
The first stable anionic aluminium nucleophile was isolated by Goicoechea, Aldridge and co‐workers. The aluminyl compound showed very high reactivity in metathesis reactions as well as in the oxidative addition of substrates such as dihydrogen and benzene, which opens up new perspectives in main group chemistry.
Article
A general synthetic protocol for the synthesis of phosphorus‐ and arsenic‐containing analogues of the thio‐ and seleno‐cyanate anions is reported. This procedure allows for the isolation of three unprecedented species: the phosphaethynselenolate, PCSe− (1), the arsaethynthiolate, AsCS− (2), and the arsaethynselenolate, AsCSe− (3), anions. The struc...
Article
A phosphino‐arsinidene derived from a diazaphospholidine scaffold (Ar**NCH2)2PAs (where Ar** = 2,6‐bis[(4‐tert‐butylphenyl)methyl]‐4‐methylphenyl) was generated in situ and trapped with a range of reagents. Metathesis reactions between (Ar**NCH2)2PCl and either [Na(18‐crown‐6)][AsCO] or [Na(dioxane)x][AsCO] are believed to afford an arsaketene, (Ar...
Article
A general synthetic protocol for the synthesis of phosphorus‐ and arsenic‐containing analogues of the thio‐ and seleno‐cyanate anions is reported. This procedure allows for the isolation of three unprecedented species: the phosphaethynselenolate, PCSe− (1), the arsaethynthiolate, AsCS− (2), and the arsaethynselenolate, AsCSe− (3), anions. The struc...
Article
The use of bulky aryl(silyl)amides (R) as substituents for the stabilisation of phospha‐germynes and phospha‐stannynes (R‐Ge≡P and R‐Sn≡P, respectively) is described. Such species can be transiently generated by photolysis of the phosphaketene precursors (RE(PCO); E = Ge, Sn). Utilisation of bulky amides R1 and R2 (R1 = Ar**NSi(OtBu)3, where Ar** =...
Article
Balancing the biradicaloid and zwitterion reactivity within one single molecule is nearly an unexplored field because both characters represent highly reactive species. Here, it is demonstrated that the dicarbondiphsphide (C2P2) stabilized with N-heterocyclic carbenes exhibited both biradicaloid and zwitterion reactivity experimentally, which is fu...
Article
Since the heavy biradicals [E(-NTer)]2 (E = Sb, Bi) are only of fleeting existence in solution, they were generated in situ and quenched by [2+2] addition reactions utilizing alkynes such...
Article
The isolation of binary As–N and ternary As–N–P cage compounds consisting exclusively of group 15 elements was achieved by exploiting the reactivity of diarsadiazanediyl. This arsenic centered biradical is capable of activating and/or quenching small molecules bearing double bonds such as diazenes, Ph–N=N–Ph, or in situ generated labile diphosphene...
Article
The synthesis and characterization of a stable phosphaethynolato-borane, [B]OCP (1, [B] = N,N'-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl), is described. The increased triple bond character of the P-C bond in 1 relative to the free ion (PCO-) is probed in a series of reactivity studies. Compound 1 readily dimerises in donor solvents...
Article
The synthesis and characterization of a stable phosphaethynolato-borane, [B]OCP (1, [B] = N,N'-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl), is described. The increased triple bond character of the P-C bond in 1 relative to the free ion (PCO-) is probed in a series of reactivity studies. Compound 1 readily dimerises in donor solvents...
Article
Organic biradicals are usually very short-lived species under standard laboratory conditions, which makes their experimental studies difficult. In contrast, heteroatom-substituted analogs of these biradicals display enhanced stability by π-electron delocalization, which is why main group biradicals (or biradicaloids) of archetypical heterocyclobuta...
Article
The reactivity of two paramagnetic nickel(I) compounds, CpNi(NHC) (where Cp = cyclopentadienyl; NHC = 1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene (IMes) or 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene (IPr)), towards [Na(dioxane)x][PnCO] (Pn = P, As) is described. These reactions afford symmetric bimetallic compounds (µ2:η2,η2-Pn2){Ni(NH...
Article
The reactivity of two paramagnetic nickel(I) compounds, CpNi(NHC) (where Cp = cyclopentadienyl; NHC = 1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene (IMes) or 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene (IPr)), towards [Na(dioxane)x][PnCO] (Pn = P, As) is described. These reactions afford symmetric bimetallic compounds (µ2:η2,η2-Pn2){Ni(NH...
Article
Alkynes usually oligomerize to give rings with a conjugated -electron system. In contrast, phosphaalkynes, R-CP, frequently give compounds with polycyclic structures which are thermodynamically more stable than the corresponding -conjugated isomers. Here we report the syntheses of the first C3P3 cages with either radical or cation ground states...
Article
Alkynes usually oligomerize to give rings with a conjugated -electron system. In contrast, phosphaalkynes, R-CP, frequently give compounds with polycyclic structures which are thermodynamically more stable than the corresponding -conjugated isomers. Here we report the syntheses of the first C3P3 cages with either radical or cation ground states...
Article
The reaction of the low melting solid PPN(N3) with copper(II) acetate in ethanol yields (PPN)2[Cu11(N3)24(C2H5OH)2]. The undecanuclear azidocuprate dianon is unprecedented and represents the largest example for a discrete azidocuprate(II) anion to date. This structurally more-or-less flat anion contains features of Cu(N3)2, i. e. can be considered...
Article
An unprecedented dichloro-cycloazatriphosphane that incorporates a cyclic NP3 backbone could be synthesized using knowledge gained from the chemistry of N2P2 and P4 ring systems. It fills the gap between the homologous compounds [ClP(µ-NR)]2 and [ClP(µ-PR)]2 (R = sterically demanding substituent), and thus contributes to the systematic development...
Article
N-heterocyclic carbene adducts of the parent arsinidene (AsH) were prepared by two different synthetic routes, either by reaction of As(SiMe3)3 with 2,2-difluoroimidazolines followed by desilylation or by reaction of [Na(dioxane)3.31][AsCO] with imidazolium chlorides.