Michael Bodensteiner

Universität Regensburg | UR · Faculty of Chemistry and Pharmacy

The extraction and purification procedures, crystallization and crystal structure refinement (single-crystal X-ray data) of germacrone type II, C15H22O, are presented. The structural results are compared with a previous powder X-ray synchrotron study [Kaduk et al. (2022). Powder Diffr. 37, 98–104], revealing significant improvements in terms of acc...

An implementation of Slater-type spherical scattering factors for X-ray and electron diffraction for elements in the range Z = 1–103 is presented within the software Olex2 . Both high- and low-angle Fourier behaviour of atomic electron density and electrostatic potential can thus be addressed, in contrast to the limited flexibility of the four Gaus...

An in‐depth analysis of the description of bonding within Cp'''Ni‐cyclo‐P3 (Cp''' = 1,2,4‐tri‐tert‐butylcyclopentadienyl, [Ni]P3) employing X‐ray diffraction based multipolar modeling, density functional theory (DFT) as well as an “experimental wavefunction” obtained from X‐ray restrained wavefunction (XRW) fitting is presented. The results are com...

The title compound, 2,6-dibromo-3,4,5-trimethoxybenzoic acid (DBrTMBA), C 10 H 10 Br 2 O 5 , was obtained by bromination and transhalogenation of 2-iodo-3,4,5-trimethoxybenzoic acid with KBrO 3 . Like the previously reported 2,6-diiodo-3,4,5-trimethoxybenzoic acid (DITMBA), the structure of the title compound features a catemeric arrangement of DBr...

The investigated co-crystal of 3-chloro- N -methylpyridinium iodide with tetrabromoquinone (3-Cl- N -MePy·I·Br 4 Q) reveals a π-hole interaction between an iodide anion and a quinoid ring involving an n → π* charge transfer. The quinoid ring has a partial negative charge (estimated to be in the range 0.08–0.11 e ) and a partial radical character, w...

An unprecedented family of three‐ and five‐membered substituted anionic derivatives of parent pnictogenylboranes is herein reported. Reacting various combinations of the pnictogenylboranes H2E′−BH2−NMe3 (E′=P, As) with pnictogen‐based nucleophiles MER1R2 (E=P, As; R1=H, R2=tBu; R1=R2=Ph; M=Na, K) allows for the isolation of the unsymmetrical produc...

Toluene solvates of MCl4·nIDipp (n = 1, M = Ge, Sn; n = 2, M = Sn) complexes have been synthesized and structurally characterized. Mass spectrometry studies indicate that upon heating complexes of a 1:1 composition MCl4·IDipp undergo sublimation and dissociation into the components, while a complex of 1:2 composition SnCl4·2IDipp does not exist in...

Two antimony complexes {[Sb(L1)Cl2] C1 and [Sb(L2)Cl2] C2} with the thiosemicarbazone ligands {HL1 = 4-(2,4-dimethylphenyl)-1-((pyridin-2-yl)methylene)thiosemicarbazide and HL2 = 4-(2,5-dimethoxyphenyl)-1-((pyridin-2-yl)methylene)thiosemicarbazide} were introduced. The structures were elucidated on the basis of a CHNS analysis, spectroscopic techni...

Correcting for anomalous dispersion is part of any refinement of an X-ray diffraction crystal structure determination. The procedure takes the inelastic scattering in the diffraction experiment into account. This X-ray absorption effect is specific to each chemical compound and is particularly sensitive to radiation energies in the region of the ab...

The crystalline sponge method facilitates the X-ray structure determination of samples that do not crystallize or are too sparsely available to afford viable crystallization. By including these materials in a metal–organic framework, the structure of the guest molecules can be determined. Some of the inherent difficulties of this method are discuss...

The crystal structures of five donor–acceptor (DA) complexes of 1:1 and 2:1 composition between E(C6F5)3 (E = B, Al, Ga and In) and pyrazine (pyz) as a non-chelating bidentate nitrogen-containing donor, as well as the GaI3 pyz GaI3 complex have been established for the first time. A joint analysis of the experimental structural data and the results...

The new mercuric complex [Hg(HL)2Cl2] incorporating salicylaldimine ligand (HL = 2‐((pyridin‐3‐ylimino)methyl)phenol) was fabricated where the ligand molecules behaved in a monodentate manner via their pyridine nitrogen atoms. In addition to elemental characterization, X‐ray crystallographic studies of the complex revealed its packing in a monoclin...

Re(CO) 5 Cl reacts with salophenH 2 to yield Re(I) 2 (salophenH)(CO) 6 Cl. A crystal structure determination has shown that this binuclear complex contains two Re(CO) 3 fragments which are bridged by a chloride and a heavily constrained salophenH – anion as ligands. Under ambient conditions in solution and in the solid state, the complex displays a...

The relationship between the structure and the properties of a drug or material is a key concept of chemistry. Knowledge of the three-dimensional structure is considered to be of such importance that almost every report of a new chemical compound is accompanied by an X-ray crystal structure – at least since the 1970s when diffraction equipment beca...

The synthesis of rare anionic heteroleptic and homoleptic α-diimine iron complexes is described. Heteroleptic BIAN (bis(aryl)iminoacenaphthene) complexes 1-[K([18]c-6)(thf)0.5] and 2-[K([18]c-6)(thf)2] were synthesized by reduction of the [(BIAN)FeBr2] precursor complex using stoichiometric amounts of potassium graphite in the presence of the corre...

The reaction of [Cp′′′Ni(η³‐P3)] (1) with in situ generated phosphenium ions [RR′P]⁺ yields the unprecedented polyphosphorus cations of the type [Cp′′′Ni(η³‐P4R2)][X] (R=Ph (2 a), Mes (2 b), Cy (2 c), 2,2′‐biphen (2 d), Me (2 e); [X]⁻=[OTf]⁻, [SbF6]⁻, [GaCl4]⁻, [BArF]⁻, [TEF]⁻) and [Cp′′′Ni(η³‐P4RCl)][TEF] (R=Ph (2 f), tBu (2 g)). In the reaction o...

Die Reaktion des Pentaphosphaferrocens [Cp*Fe(η⁵‐P5)] (1) mit kationischen Elektrophilen führt zur Bildung der Komplexe [Cp*Fe(η⁵‐P5R)][B(C6F5)4] (R=SiEt3, H, Me). Diese Verbindungen stellen die ersten strukturell charakterisierten Koordinationsverbindungen dar, die über die schwer fassbaren Pentaphosphole (cyclo‐P5R) als Liganden, einschließlich d...

Electrophilic functionalisation of [Cp*Fe(η⁵‐P5)] (1) yields the first transition‐metal complexes of pentaphospholes (cyclo‐P5R). Silylation of 1 with [(Et3Si)2(μ‐H)][B(C6F5)4] leads to the ionic species [Cp*Fe(η⁵‐P5SiEt3)][B(C6F5)4] (2), whose subsequent reaction with H2O yields the parent compound [Cp*Fe(η⁵‐P5H)][B(C6F5)4] (3). The synthesis of a...

Di‐tert‐butyldiphosphatetrahedran, ein tetraedrisches Molekül aus Phosphor‐ und Kohlenstoffatomen, wird von R. Wolf und Mitarbeitern in ihrer Zuschrift vorgestellt (DOI: 10.1002/ange.201910505). Die metastabile Verbindung wurde zuvor durch theoretische Berechnungen als Schlüsselintermediat in der Oligomerisierung von Phosphaalkinen vorhergesagt. Di...

Endlich frei: Di‐tert‐butyldiphosphatetrahedran ist durch die nickelkatalysierte Dimerisierung von tert‐Butylphosphaalkin zugänglich. Diese Verbindung stellt das seit langem postulierte freie Phosphaalkindimer dar und ist zudem das erste Beispiel für ein isolierbares Tetrahedran mit Kohlenstoff‐ und Phosphoratomen im Tetraedergerüst. Abstract Die...

While tetrahedranes as a family are scarce, neutral heteroatomic species are all but unknown, with the only reported example being AsP3. Herein, we describe the isolation of a neutral heteroatomic X2Y2 molecular tetrahedron (X, Y=p‐block elements), which also is the long‐sought‐after free phosphaalkyne dimer. Di‐tert‐butyldiphosphatetrahedrane, (tB...

Di‐tert‐butyldiphosphatetrahedrane, a tetrahedral molecule comprised of phosphorus and carbon atoms, is described by R. Wolf and co‐workers in their Communication (DOI: 10.1002/anie.201910505). This metastable compound was previously predicted by theoretical calculations as a key intermediate in the oligomerization of phosphaalkynes. The synthesis...

Schwer fassbares HAs=AsH, das schwere Analogon von Ethylen, wurde ohne kinetische Stabilisierung durch einen 3d‐Übergangsmetallkomplex koordiniert. Durch Methanolyse von [{Fe(CO)4}As(SiMe3)3] wurde der Komplex [{Fe(CO)4}{η²‐As2H2}] synthetisiert. DFT‐Rechnungen zeigen, dass der Bindungsmodus am besten mit dem Dewar‐Chatt‐Duncanson‐Modell beschriebe...

The terminal diarsene HAs=AsH ligand attracts special interest concerning its bonding relation in comparison to its isolable relative, ethene. Herein, by the methanolysis of [{Fe(CO)4}As(SiMe3)3] (1) the synthesis of [{Fe(CO)4}(η²‐As2H2)] (2) is reported, containing a parent diarsene as unprecedented side‐on coordinated ligand. Following this synth...

We report on the design, synthesis, characterization and successful application of a heterodinuclear Ir(III)/Pt(II) complex endowed with two 4,6-diphenylpyrimidine ligands and two acetylacetonate ligands, with one of the former being the rigid bridging unit between the two metal centers. The heterodinuclear complex exhibits red phosphorescence with...

Redox non-innocent ligands are a promising tool to moderate electron transfer processes within base-metal catalysts. This report introduces bis(imino)acenaphthene (BIAN) cobaltate complexes as hydrogenation catalysts. Sterically hindered tri-substituted alkenes, imines, and quinolines underwent clean hydrogenation under mild conditions (2-10 bar, 2...

We report on the photophysical properties of three dyads that combine a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (bodipy, BDP) and a mercaptopyrene (SPyr) dye ligand at a Pt(PEt3)2 fragment. -Bonding of the dyes to the Pt ion promotes intersystem crossing (ISC) via the external heavy atom effect. The coupling of efficient ISC with charge-transfe...

The salt [Rh(III)(phpy) 2 (dtoxa)]Cl with phpy = 2-(2-pyridyl)phenyl anion and dtoxa = dithiooxamide has been characterized by its crystal structure and its electronic spectra. Since Rh(III) is rather redox-inert, the lowest-energy excited state of the complex cation is of the IL (dtoxa) type. In the solid state as well as in solution the complex i...

The structural and photophysical properties of a series of new Au(I) compounds have been studied. The reactions of AuCl(tht) with the phosphanyl‐ and arsanylboranes RR'EBH2NMe3 (E = P, As; R = H, Ph; R' = H, Ph, tBu) afford the complexes [AuCl(RR'EBH2NMe3)]. In the solid state, [AuCl(H2PBH2NMe3)]2 (2a) is a dimer showing unsupported intermolecular...

The binuclear complex Re(I) 2 ( μ -4,4′-bipyridine)(8-quinolinolato) 2 (CO) 6 has been prepared and characterized including the crystal structure. This complex shows, dependent on the conditions, three emissions, which originate from the quinolinolate IL excited state (fluorescence and phosphorescence) and from a Re(I) to 4,4′-bipyridine MLCT state...

Reduction of [CpArFe(μ Br)]2 (1, CpAr = C5(C6H4-4-Et)5) by potassium napthalenide, followed by the addition of white phosphorus, affords [K(18-c-6){CpArFe(η4-P4)}] (2, 18-c-6 = [18]crown-6), which features a planar cyclo-P42- ligand. The related diiron complex [Na2(THF)5(CpArFe)2(μ,η4:4-P4)] (3) was obtained by reducing 1 with sodium amalgam in the...

Hydrogen bond patterns of crystals of phosphinic, phosphonic, and phosphoric acids and their co-crystals with phosphine oxides were studied using 31P NMR and single-crystal XRD. Two main factors govern these patterns and favor or prevent the formation of co-crystals. The first one is a high proton-accepting ability of the P=O moiety in these acids....

We report on depolymerization reactions of poly(phosphinoboranes). The cleavage of the polymers [H2PBH2]n (2a), [tBuHPBH2]n (2c), [PhHPBH2]n (2e) and the oligomer [Ph2PBH2]n (2b), with strong Lewis bases, in particular with NHCs, leads to the corresponding monomeric phosphanylboranes R1R2PBH2LB. It is observed that the depolymerization depends on t...

Ethynyl-2-furancarboxylic acid or 3-ethynylbenzoic acid self-assemble with HRu(CO)Cl(PiPr3)2 to macrocyclic C3-symmetric triangular triruthenium alkenyl complexes {Ru(CO)(PiPr3)2(CH=CH-Ar-COO)}3 (Ar = C6H4: 1-B, Ar = C4H2O: 1-F). The latter have been characterized by multinuclear NMR spectroscopy, high-resolution ESI-MS mass spectrometry and, in th...

Treatment of NiCl2 with the tripod ligand (LMent,SC)-1H led to (LMent,SC)-[Cp(PNMent)NiCl] in which the potentially tridentate ligand coordinated to the metal center in a bidentate way via the cyclopentadienyl system and the phosphorus atom. In the presence of NH4PF6[(LMent,SC)-[Cp(PNMent)NiCl] readily underwent Cl/PPh3 exchange to give (LMent,SC)-...

The co-thermolysis of As4 and [Cp''2Zr(CO)2] (Cp'' = η5-C5H3tBu2) results in the formation of [Cp''2Zr(η1:1-As4)] (1) in high yields and the arsenic-rich complex [(Cp''2Zr)(Cp''Zr)(µ,η2:2:1-As5)] (2) as a minor product. In contrast to yellow arsenic, 1 is a light-stable, weighable and storable arsenic source for subsequent reactions. This is demons...

The versatile coordination behavior of [Cp′′2Zr(η1:1-P4)] is investigated. Lewis acidic fragments of tungsten, manganese, iron and aluminum are used to study their influence on the coordination behavior towards [Cp′′2Zr(η1:1-P4)], which strongly depends on the steric and electronic properties of the used Lewis acids. The cover picture highlights th...

The redox chemistry of [Cp*Fe(η(5) -As5 )] (1, Cp*=η(5) -C5 Me5 ) has been investigated by cyclic voltammetry, revealing a redox behavior similar to that of its lighter congener [Cp*Fe(η(5) -P5 )]. However, the subsequent chemical reduction of 1 by KH led to the formation of a mixture of novel Asn scaffolds with n up to 18 that are stabilized only...

Die Untersuchung der Redoxchemie von [Cp*Fe(η5-As5)] (1) (Cp*=η5-C5Me5) mittels Cyclovoltammetrie ergab ein Redoxverhalten, das jenem des leichteren Verwandten [Cp*Fe(η5-P5)] ähnelt. Die anschließende chemische Reduktion von 1 durch KH führt zur Bildung eines Gemisches von Produkten mit neuartigen Asn-Gerüsten (n=bis zu 18), die lediglich durch [Cp...

A detailed method for the preparation of [Cp''2Zr(η1:1-P4)] (1) is presented. The coordination behavior of 1 towards Lewis acidic transition metal complexes of tungsten, manganese and iron, respectively, and main group compounds (AlMe3, AlEt3) was investigated in detail by computational and experimental studies. In doing so, a series of unprecedent...

The crystal structure of cannabidiol, C 21 H 30 O 2 , {systematic name: 2-[(1 R ,6 R )-3-methyl-6-(prop-1-en-2-yl)cyclohex-2-enyl]-5-pentylbenzene-1,3-diol}, was determined earlier by Jones et al. [(1977). Acta Cryst. B 33 , 3211–3214] and Ottersen & Rosenqvist [(1977). Acta Chem. Scand.B31 , 749–755]. In both investigations, the absolute configura...

Sterically demanding N,N′,N′-substituted 1,2-ethanediamine ligands have been prepared from commercially available starting materials by applying a facile one-step procedure. These ligands offer advantages compared to known systems: a suppressed delocalization due to the saturated backbone inhibits a noninnocent behaviour and the low symmetry of the...

Invited for the cover of this issue is the group of Takashi Tsuno from Nihon University, Narashino, Japan, in collaboration with the group of Henri Brunner from Universität Regensburg, Germany. The cover image shows two pairs of half-sandwich (RM,RC)/(SM,RC) diastereomers that co-crystallize, although each diastereomer should crystallize in its own...

The cover picture shows two pairs of half-sandwich (RM,RC)/(SM,RC) diastereomers that co-crystallize, although each diastereomer should crystallize in its own lattice. The (SFe,RC) diastereomer of the Fe pair with the “red” Fe configuration imitates the (RFe,RC) diastereomer with the “sky-blue” Fe configuration to become its “almost enantiomer” in...

Inspired by VUF6884 (7-Chloro-11-(4-methylpiperazin-1-yl)dibenzo[b,f][1,4]oxazepine), reported as a dual H1/H4 receptor ligand (pKi: 8.11 (human H1R (hH1R)), 7.55 (human H4R (hH4R))), four known and 28 new oxazepine and related oxepine derivatives were synthesised and pharmacologically characterized at histamine receptors and selected aminergic GPC...

We report on the synthesis and structural characterization of unprecedented anionic parent compounds of mixed Group 13/15 elements. The reactions of the pnictogenylboranes H2 E-BH2 ⋅NMe3 (1 a=P, 1 b=As) with phosphorus and arsenic centered nucleophiles of the type [EH2 ](-) (E=P, As) lead to the formation of compounds of the type [H2 E-BH2 -E'H2 ](...

Wir berichten über die Synthese und strukturelle Charakterisierung von präzedenzlosen anionischen Stammverbindungen aus gemischten Elementen der Gruppen 13 und 15. Die Reaktionen der Pnictogenylborane H2E-BH2⋅NMe3 (1 a: E=P; 1 b: E=As) mit phosphor- und arsenzentrierten Nukleophilen der Form [EH2]− (E=P, As) führen zur Bildung von Verbindungen des...

Diastereomer separation by fractional crystallization is the most important method for the resolution of enantiomers in research as well as in industry. Herein we describe two different types of diastereomer co-crystallization, which impede diastereomer separation. - The two diastereomers (RFe,RC)- and (SFe,RC)-[CpFe(Prophos)PPh(OMe)2]PF6, differin...

Photophysical properties of four new platinum(II) complexes comprising extended ppy (Hppy = 2-phenylpyridine) and thpy (Hthpy = 2-(2'-thienyl)pyridine) cyclometalated ligands and acetylacetonate (acac) are reported. Substitution of the benzene ring of Pt-ppy complexes 1 and 2 with a more electron-rich thiophene of Pt-thpy complexes 3 and 4 leads to...

The effect of hydrogen bonding to water on the 31P NMR chemical shift tensor in the titled compounds has been studied experimentally and simulated theoretically using the DFT-GIAO approach. It has been shown that the effect of hydrogen bonding on the 31P NMR parameters of trialkylphosphine oxides can be simulated at the GIAO-B3LYP/cc-pVDZ approxima...

The preparation of new stable half-sandwich transition metal complexes, having a bulky cyclopentadienyl ligand C5(C6H4-4-Et)5 (Cp(Ar1)) or C5(C6H4-4-nBu)5 (Cp(Ar2)), is reported. The tetrahydrofuran (THF) adduct [Cp(Ar1)Fe(μ-Br)(THF)]2 (1a) was synthesized by reacting K[Cp(Ar1)] with [FeBr2(THF)2] in THF, and its molecular structure was determined...

A high-yielding and facile synthesis for diphosphane monochalcogenides (1Ch(R)) and their constitutional isomers, diphosphanylchalcoganes (2Ch(R)), was developed, featuring a condensation reaction between chlorophosphanes (R2PCl) and sodium chalcogenides (Na2Ch, Ch = S, Se, (Te)). The optimized protocol selectively yields either 1Ch(R) (R2(Ch)PPR2)...

The reaction of titanium tetrachloride with diethyl ether at various ratios of components and temperatures was studied by the NMR and mass spectrometry methods. The TiCl4·2Et2O complex does not pass in the gas phase. Formation of ethoxytrichlorotitanium among reaction products was established by the X-ray structure analysis. The model of conversion...

A systematic structural study of complexes formed by aluminium and gallium trihalides with 4,4'-bipyridine (bipy) in 2 : 1, 1 : 1, and 1 : 2 stoichiometric ratios has been performed. Molecular structures of 11 complexes in the solid state have been determined for the first time. Complexes of 2 : 1 composition are molecular, while complexes of 1 : 1...

The first 4d/4f polyphosphides were obtained by reaction of the divalent metallocenes [Cp*2Ln(thf)2] (Ln = Sm, Yb) with [{CpMo(CO)2}2(μ,η2:2-P2)] or [Cp*Mo(CO)2(η3-P3)]. Treatment of [Cp*2Ln(thf)2] (Ln = Sm, Yb) with [{CpMo(CO)2}2(μ,η2:2-P2)] gave the 16-membered bicyclic compounds [(Cp2*Ln)2P2(CpMo(CO)2)4] (Ln = Sm, Yb) as the major products. From...

The synthesis of the Lewis base stabilized monomeric parent compound of stibanylboranes, "H2 SbBH2 ", is reported. Through a salt metathesis route, the silyl-substituted compounds (Me3 Si)2 SbBH2 ⋅LB (LB=NMe3 , NHC(Me) ) were synthesized as representatives of derivatives with a SbB σ bond. Under very mild conditions, they could be transformed in...

Wir berichten über die Synthese der Lewis-Base-stabilisierten monomeren Stammverbindung des Stibanylborans, “H2Sb-BH2”. Über eine Salzmetathese wurden die silylsubstituierten Verbindungen (Me3Si)2Sb-BH2⋅LB (LB=NMe3, NHCMe) synthetisiert, die Derivate mit einer Sb-B-σ-Bindung repräsentieren. Unter sehr milden Bedingungen konnten sie in die Zielverbi...

The use of the highly sterically demanding Cp(BIG) ligand (Cp(BIG) = C5(4-nBuC6H4)5) and white phosphorus (P4) enables the synthesis of new P-rich derivatives of the rare Pn ligand complexes of manganese. The obtained complexes, [{Cp(BIG)Mn}2(μ,η(5:5)-P5)] () and [{Cp(BIG)Mn}2(μ,η(2:2)-P2)2] (), exhibit the highest number of P atoms in this class o...

To vary the substitution pattern of 1,2,4-triphospholyl ligands, K[P(3)C(2)Mes(2)] (Mes=2,4,6-trimethylphenyl), bearing two bulky mesityl ligands, was synthesized. Subsequent reaction with [FeBr2(dme)] and LiCp* results in the formation of the corresponding triphosphaferrocene [Cp*Fe(eta(5)-P(3)C(2)Mes(2))] (1) in very good yields. P-31{H-1} NMR in...

The potassium salt [K([18]crown-6)(THF)2][Cp*Fe(η4-2,4,6-triphenylphosphinine)}] (K1, Cp* = C5Me5) can be isolated in 68% yield by reacting the anionic naphthalene complex [K([18]crown-6){Cp*Fe(η4-C10H8)}] (C10H8 = naphthalene) with 2,4,6-triphenylphosphinine. Compound K1 reacts with water to afford [K([18]-crown-6)]{Cp*Fe(η4-2,4,6-triphenyl-2,3-di...

The reaction of the phosphinidene and arsinidene complexes [Cp*E{W(CO)5}2] (E=P (1 a), As (1 b); Cp*=C5Me5) with carbodiimides leads to the new four-membered heterocycles of the type [Cp*C(NR)2E{W(CO)5}2] (E=P: R=iPr (2 a), Cy (3 a); E=As: R=iPr (2 b), Cy (3 b)). The reaction of phosphinidene complex 1 a with alkyl azides yields the triazaphosphete...

Die Reaktion der Pentelidenkomplexe [Cp*E{W(CO)5}2] (E=P (1 a), As (1 b); Cp*=C5Me5) mit Carbodiimiden führt zu den neuen viergliedrigen Heterocyclen des Typs [Cp*C(NR)2E{W(CO)5}2] (E=P: R=iPr (2 a), Cy (3 a); E=As: R=iPr (2 b), Cy (3 b)). Die Reaktion des Phosphinidenkomplexes 1 a mit Alkylaziden ergibt die Triazaphosphetderivate [Cp*P{W(CO)5}N(R)...

The reaction of [{η5-Cp'''Co}2{μ,η4:4-toluene}] with yellow arsenic yields the arsenic-rich As n ligand complexes [{Cp'''Co(μ,η2:2-As2)}2] (1), [(Cp'''Co)4(μ4,η4:4:2:2:1:1-As10)] (2) and [(Cp'''Co)3(μ3,η4:4:2:1-As12)] (3), which were comprehensively characterized. The molecular structure of1show a triple-decker complex with two As2units forming the...

In 1,2-Me,Ph substitution patterns of organic compounds the methyl group attracts one of the phenyl sides to establish a CH/π bond with one of the ortho carbon atoms (the Co side), leading to a characteristic tilting of the phenyl ring around its Ci–Cp axis. This phenyl rotation shortens the CMe–Co distances to bonding contacts between the methyl h...

Compound Ph3As(OTf)2 as a pentacoordinated AsV Lewis acid readily forms dicationic Lewis acid/base adducts upon addition of various Lewis bases. It also represents a stronger chloride-abstracting agent than Me3SiOTf and facilitates the reductive coupling of PCl3 in the presence of AsPh3 to the unprecedented cation [P7(AsPh3)3]3+ as triflate salt. T...

P-H functional transition-metal complexes were synthesized without using hazardous PH3 gas in good yields by photolysis of the transition-metal carbonyl complexes M(CO)6-x (M = Cr, W, Fe; x = 0, 1) in tetrahydrofuran followed by reaction with P2(SiMe3)4 and subsequent methanolysis to give the bridging complexes [(CO)xM(μ-PH2)]2 (M = Fe, x = 3 (1),...

A new and selective one-step synthesis was developed for the first activation stage of white phosphorus by organic radicals. The reactions of NaCp(R) with P4 in the presence of CuX or FeBr3 leads to the clean formation of organic substituted P4 butterfly compounds Cp(R) 2 P4 (Cp(R) : Cp(BIG) =C5 (4-nBuC6 H4 )5 (1 a), Cp'''=C5 H2 tBu3 (1 b), Cp*=C5...

Eine neue einstufige und selektive Synthese für den ersten Schritt der Aktivierung von weißem Phosphor wurde unter Verwendung organischer Radikale entwickelt. Die Reaktion von NaCpR mit P4 in Gegenwart von CuX oder FeBr3 führt zur direkten Bildung der organisch substituierten P4-Butterfly-Verbindungen CpR2P4 (CpR: CpBIG=C5(4-nBuC6H4)5 (1 a), Cp′′′=...

In the title compound, C 18 H 14 N 4 O 2 , the triazole ring makes dihedral angles of 77.32 (8) and 75.56 (9)°, respectively, with the indoline residue and the terminal phenyl group. In the crystal, molecules are linked by C—H...N hydrogen bonds into tapes parallel to the b axis. The tapes are linked together by π–π interactions between triazole ri...

The Cambridge Structural Database comprises 89 structures with M–Prosphos chelate rings. On this basis a compilation analysis of the conformation of the M–Prophos chelate ring has been carried out. Typical conformational features, such as the puckering of the chelate ring and the arrangement of the phenyl rings, important for the transmission of th...

Whilst catena-phosphorus cations have been intensively studied in the last years, mixed Group 13/15 element cationic chains have not yet been reported. Reaction of the pnictogenboranes H2 EBH2 ⋅NMe3 (E=P, As) with monohalideboranes lead to the cationic chain compounds [Me3 N⋅BH2 EH2 BH2 ⋅NMe3 ][X] (E=P, As; X=AlCl4 , I) and [Me3 N⋅BH2 PH2 BH2 PH2 B...

Während catena-Phosphorkationen innerhalb der letzten Jahre intensiv untersucht wurden, gab es über gemischte kationische Ketten aus Gruppe-13- und Gruppe-15-Elementen bislang keine Berichte. Die Umsetzung der Pnictogenborane H2EBH2⋅NMe3 (E=P, As) mit Monohalogenboranen führt zu den kationischen Kettenverbindungen [Me3N⋅BH2EH2BH2⋅NMe3][X] (E=P, As;...

Invited for the cover of this issue is the group of Manfred Scheer at the University of Regensburg. The cover image shows organometallic and inorganic building blocks being combined to form unprecedented new species.

1,3-Diphosphacyclobutadiene complexes have previously been employed as metalloligands to a few transition metals such as tungsten, cobalt, rhodium, platinum, and gold. Here, we describe the synthesis and the structural and spectroscopic characterization of novel copper(I) and silver(I) complexes with the sandwich anions [Co(η4-P2C2R2)2]– (R = tBu o...

By using [(Cp″′Co)2tol] (Cp″′ = η5-C5H2tBu3, tol = toluene), a new synthesis of the 1,3-diphosphete complexes [Cp″′Co(η4-P2C2tBu2)] (1a) and [Cp″′Co(η4-P2C2iPr2)] (1b) was found, and their reactions with the Lewis acids W(CO)4 and CuI halides were investigated. The reaction of 1b with W(CO)4(nbd) (nbd = norbornadiene) leads to the complex [(Cp″′Co)...

A giant quasi-spherical supramolecule [{Cp*Fe(η5-P5)}12(CuBr)18.8] encapsulating o-carborane was prepared by the reaction between CuBr and [Cp*Fe(η5-P5)] (Cp* = pentamethylcyclopentadienyl) and structurally characterized. The crystal structure can be treated as solid solution of various [(Cp*Fe(η5-P5))12(CuBr)n] supramolecules with n = 18–20. Two c...

Chromium(II) chloride reacts with lithium pentamethylcyclopentadienide (LiCp*, Cp* = C5Me5) and LiE(SiMe3)2 (E = P or As) to give the heterocubane chromium phosphide [(η5-Cp*Cr)(μ3-P)]4 (1) or the chromium arsenide cage [(η5-Cp*Cr)3(μ3-As)2] (2), respectively. The crystal and molecular structures of both compounds have been determined by X-ray crys...

Reactions of the sandwich complexes [Cp*Fe(η(5) -E5 )] (Cp*=η(5) -C5 Me5 ; E=P (1), As (2)) with the monovalent Group 13 metals Tl(+) , In(+) , and Ga(+) containing the weakly coordinating anion [TEF] ([TEF]=[Al{OC(CF3 )3 }4 ](-) ) are described. Here, the one-dimensional coordination polymers [M(μ,η(5) :η(1) -E5 FeCp*)3 ]n [TEF]n (E=P, M=Tl (3 a),...

The molecular structures of trichlorido(2,2':6',2''-terpyridine-κ(3)N,N',N'')gallium(III), [GaCl3(C15H11N3)], and tribromido(2,2':6',2''-terpyridine-κ(3)N,N',N'')gallium(III), [GaBr3(C15H11N3)], are isostructural, with the Ga(III) atom displaying an octahedral geometry. It is shown that the Ga-N distances in the two complexes are the same within ex...

Molecular squares are among the most common supramolecular architectures, but phospha-organometallic complexes have not been used as building blocks for this type of structure. Herein we describe the formation of the molecular square [Au{Co(P2 C2 tBu2 )2 }]4 (1) by the self-assembly of anionic 1,3-diphosphacyclobutadiene cobalt complexes and gold(I...