Redetermination of germacrone type II based on single-crystal X-ray data.

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 accuracy and precision. Hirshfeld atom refinement (HAR), as well as Hirshfeld surface analysis, give insight into the inter-molecular inter-actions of germacrone type II.

Refinement of X-ray and electron diffraction crystal structures using analytical Fourier transforms of Slater-type atomic wavefunctions in Olex2.

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 Gaussian plus constant descriptions which are currently the most widely used method for calculating atomic scattering factors during refinement. The implementation presented here accommodates the increasing complexity of the electronic structure of heavier elements by using complete atomic wavefunctions without any interpolation between precalculated tables or intermediate fitting functions. Atomic wavefunctions for singly charged ions are implemented and made accessible, and these show drastic changes in electron diffraction scattering factors compared with the neutral atom. A comparison between the two different spherical models of neutral atoms is presented as an example for four different kinds of X-ray and two electron diffraction structures, and comparisons of refinement results using the existing diffraction data are discussed. A systematic but slight improvement in R values and residual densities can be observed when using the new scattering factors, and this is discussed relative to effects on the atomic displacement parameters and atomic positions, which are prominent near the heavier elements in a structure.

Probing the Isolobal Relation between Cp'''NiP3 and White Phosphorus by Experimental Charge Density Analysis.

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 compared to DFT calculations on white phosphorus - an isolobal analogue to [Ni]P3. A complementary bonding analysis shows insights into the reactivity of [Ni]P3. The isolobal principle is reflected in every aspect of our analysis and the employed methods seamlessly predict the differences in reactivity of [Ni]P3 and P4. Crystallographic modeling, solid-state NMR, and DFT calculations describe the dynamic behavior of the cyclo-P3 unit in the title molecule.

2,6-Di-bromo-3,4,5-tri-meth-oxy-benzoic acid.

The title compound, 2,6-di-bromo-3,4,5-tri-meth-oxy-benzoic acid (DBrTMBA), C10H10Br2O5, was obtained by bromination and transhalogenation of 2-iodo-3,4,5-tri-meth-oxy-benzoic acid with KBrO3. Like the previously reported 2,6-di-iodo-3,4,5-tri-meth-oxy-benzoic acid (DITMBA), the structure of the title compound features a catemeric arrangement of DBrTMBA mol-ecules along an endless chain of carb-oxy-lic H-carbonyl inter-actions. A short carbon-yl-phenyl contact hints at a possible lone pair(O)-π-hole inter-action further stabilizing the chain-like structure over a dimeric arrangement of the carb-oxy-lic acid.

The nature of π-hole interactions between iodide anions and quinoid rings in the crystalline state.

The investigated co-crystal of 3-chloro-N-methylpyridinium iodide with tetrabromoquinone (3-Cl-N-MePy·I·Br4Q) 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 0.08-0.11e) and a partial radical character, which is related to the black colour of the crystals (crystals of neutral tetrabromoquinone are yellow). A detailed X-ray charge density study revealed two symmetry-independent bond critical points between the iodide anions and carbon atoms of the ring. Their maximum electron density of 0.065 e Å-3 was reproduced by quantum chemical modelling. The energy of the interaction is estimated to be -11.16 kcal mol-1, which is comparable to the strength of moderate hydrogen bonding (about -10 kcal mol-1); it is dominantly electrostatic in nature, with a considerable dispersion component.

Three- and Five-Membered Anionic Chains of Pnictogenylboranes.

An unprecedented family of three- and five-membered substituted anionic derivatives of parent pnictogenylboranes is herein reported. Reacting various combinations of the pnictogenylboranes H2 E'-BH2 -NMe3 (E'=P, As) with pnictogen-based nucleophiles MER1R2 (E=P, As; R1=H, R2=t Bu; R1=R2=Ph; M=Na, K) allows for the isolation of the unsymmetrical products [Na(18-crown-6)][H2 E'-BH2 -EHt Bu] (3: E=E'=P; 4: E=E'=As; 5: E=As, E'=P) and [M(C)][H2 E'-BH2 -EPh2 ] (7: E=E'=P, M=Na, C=18-crown-6; 8: E=E'=As; M=K, C=[2.2.2]cryptand; 9: E=P, E'=As, M=Na, C=[2.2.2]cryptand; 10: E=As, E'=P, M=K, C=[2.2.2]cryptand). [Na(18-crown-6)][H2 As-BH2 -t BuPH-BH3 ] (6) is only accessible by a different pathway, using t BuPH2 , BH3 ⋅ SMe2 and NaNH2 as starting materials. Additionally, the synthesis of symmetrical diphenyl-substituted compounds [M(18-crown-6)][Ph2 E-BH2 -EPh2 ] (11: E=P, M=Na; 12: E=As, M=K) is reported which can be regarded as isostructural inorganic, negatively charged analogs of dppm (1,1-bis(diphenylphosphino)methane) and dpam (1,1-bis(diphenylarsino)methane). Furthermore, an elongation of the pnictogen boron backbone in compounds 3, 7 and 9' (similar compound to 9, stabilized however by 18-crown-6), is attainable by reacting them with the pnictogenylboranes H2 E'-BH2 -NMe3 leading to corresponding five-membered chain-like compounds [Na(18-crown-6)][H2 E-BH2 -R1R2P-BH2 -E'H2 ] (E=E'=P, R1=H, R2=t Bu (13); E=E'=P, R1=R2=Ph (14); E=E'=As, R1=R2=Ph (15); E=P, E'=As, R1=R2=Ph (16)). Finally, the thermodynamics of the reaction pathways were evaluated by quantum chemical computations.

Refinement of anomalous dispersion correction parameters in single-crystal structure determinations.

Correcting for anomalous dispersion is part of any refinement of an X-ray dif-fraction 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 absorption edges of the elements in the compound. Therefore, the widely used tabulated values for these corrections can only be approximations as they are based on calculations for isolated atoms. Features of the unique spatial and electronic environment that are directly related to the anomalous dispersion are ignored, although these can be observed spectroscopically. This significantly affects the fit between the crystallographic model and the measured intensities when the excitation wavelength in an X-ray diffraction experiment is close to an element's absorption edge. Herein, we report on synchrotron multi-wavelength single-crystal X-ray diffraction, as well as X-ray absorption spectroscopy experiments which we performed on the mol-ecular compound Mo(CO)6 at energies around the molybdenum K edge. The dispersive (f') and absorptive (f'') terms of the anomalous dispersion can be refined as independent parameters in the full-matrix least-squares refinement. This procedure has been implemented as a new feature in the well-established OLEX2 software suite. These refined parameters are in good agreement with the independently recorded X-ray absorption spectrum. The resulting crystallographic models show significant improvement compared to those employing tabulated values.

The benefits of Cu Kß radiation for the single-crystal X-ray structure determination of crystalline sponges.

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 discussed and the use of Cu Kß radiation is presented as a simple and effective means to improve the quality of the diffraction data that can be obtained from a sponge crystal.

Paramagnetic Molecular Semiconductors Combining Anisotropic Magnetic Ions with TCNQ Radical Anions.

We report the synthesis, magnetic properties, and transport properties of paramagnetic metal complexes, [Co(DMF)4(TCNQ)2](TCNQ)2 (1), [La(DMF)8(TCNQ)](TCNQ)5 (2), and [Nd(DMF)7(TCNQ)](TCNQ)5 (3) (DMF = N,N-dimethylformamide, TCNQ = 7,7,8,8-tetracyanoquinodimethane). All three compounds contain fractionally charged TCNQδ- anions (0 < δ < 1) and mononuclear complex cations in which the coordination environment of a metal center includes several DMF molecules and one or two terminally coordinated TCNQδ- anions. The coordinated TCNQδ- anions participate in π-π stacking interactions with noncoordinated TCNQδ- anions, forming columnar substructures that provide efficient charge-transporting pathways. As a result, temperature-dependent conductivity measurements demonstrate that all three compounds exhibit semiconducting behavior.

Low-Valence Anionic α-Diimine Iron Complexes: Synthesis, Characterization, and Catalytic Hydroboration Studies.

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 corresponding olefin. The electronic structure of these paramagnetic species was investigated by numerous spectroscopic analyses (NMR, EPR, 57Fe Mössbauer, UV-vis), magnetic measurements (Evans NMR method, SQUID), and theoretical techniques (DFT, CASSCF). Whereas anion 1 is a low-spin complex, anion 2 consists of an intermediate-spin Fe(III) center. Both complexes are efficient precatalysts for the hydroboration of carbonyl compounds under mild reaction conditions. The reaction of bis(anthracene) ferrate(1-) gave the homoleptic BIAN complex 3-[K([18]c-6)(thf)], which is less catalytically active. The electronic structure was elucidated with the same techniques as described for complexes 1-[K([18]c-6)(thf)0.5] and 2-[K([18]c-6)(thf)2] and revealed an Fe(II) species in a quartet ground state.

Cationic Functionalisation by Phosphenium Ion Insertion.

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 -P4 R2 )][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 -P4 RCl)][TEF] (R=Ph (2 f), tBu (2 g)). In the reaction of 1 with [Br2 P]+ , an analogous compound is observed only as an intermediate and the final product is an unexpected dinuclear complex [{Cp'''Ni}2 (µ,η3 :η1 :η1 -P4 Br3 )][TEF] (3 a). A similar product [{Cp'''Ni}2 (µ,η3 :η1 :η1 -P4 (2,2'-biphen)Cl)][GaCl4 ] (3 b) is obtained, when 2 d[GaCl4 ] is kept in solution for prolonged times. Although the central structural motif of 2 a-g consists of a "butterfly-like" folded P4 ring attached to a {Cp'''Ni} fragment, the structures of 3 a and 3 b exhibit a unique asymmetrically substituted and distorted P4 chain stabilised by two {Cp'''Ni} fragments. Additional DFT calculations shed light on the reaction pathway for the formation of 2 a-2 g and the bonding situation in 3 a.

Stabilization of Pentaphospholes as η5 -Coordinating Ligands.

Electrophilic functionalisation of [Cp*Fe(η5 -P5 )] (1) yields the first transition-metal complexes of pentaphospholes (cyclo-P5 R). Silylation of 1 with [(Et3 Si)2 (µ-H)][B(C6 F5 )4 ] leads to the ionic species [Cp*Fe(η5 -P5 SiEt3 )][B(C6 F5 )4 ] (2), whose subsequent reaction with H2 O yields the parent compound [Cp*Fe(η5 -P5 H)][B(C6 F5 )4 ] (3). The synthesis of a carbon-substituted derivative [Cp*Fe(η5 -P5 Me)][X] ([X]- =[FB(C6 F5 )3 ]- (4 a), [B(C6 F5 )4 ]- (4 b)) is achieved by methylation of 1 employing [Me3 O][BF4 ] and B(C6 F5 )3 or a combination of MeOTf and [Li(OEt2 )2 ][B(C6 F5 )4 ]. The structural characterisation of these compounds reveals a slight envelope structure for the cyclo-P5 R ligand. Detailed NMR-spectroscopic studies suggest a highly dynamic behaviour and thus a distinct lability for 2 and 3 in solution. DFT calculations shed light on the electronic structure and bonding situation of this unprecedented class of compounds.

Accurate crystal structures and chemical properties from NoSpherA2.

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 became widely available. Crystallographic software of that time was restricted to very limited computing power, and therefore drastic simplifications had to be made. It is these simplifications that make the determination of the correct structure, especially when it comes to hydrogen atoms, virtually impossible. We have devised a robust and fast system where modern chemical structure models replace the old assumptions, leading to correct structures from the model refinement against standard in-house diffraction data using no more than widely available software and desktop computing power. We call this system NoSpherA2 (Non-Spherical Atoms in Olex2). We explain the theoretical background of this technique and demonstrate the far-reaching effects that the improved structure quality that is now routinely available can have on the interpretation of chemical problems exemplified by five selected examples.

Di-tert-butyldiphosphatetrahedrane: Catalytic Synthesis of the Elusive Phosphaalkyne Dimer.

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 X2 Y2 molecular tetrahedron (X, Y=p-block elements), which also is the long-sought-after free phosphaalkyne dimer. Di-tert-butyldiphosphatetrahedrane, (tBuCP)2 , is formed from the monomer tBuCP in a nickel-catalyzed dimerization reaction using [(NHC)Ni(CO)3 ] (NHC=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (IMes) and 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene (IPr)). Single-crystal X-ray structure determination of a silver(I) complex confirms the structure of (tBuCP)2 . The influence of the N-heterocyclic carbene ligand on the catalytic reaction was investigated, and a mechanism was elucidated using a combination of synthetic and kinetic studies and quantum chemical calculations.

The Parent Diarsene HAs=AsH as Side-on Bound Ligand in an Iron Carbonyl Complex.

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 -As2 H2 )] (2) is reported, containing a parent diarsene as unprecedented side-on coordinated ligand. Following this synthetic route, also the D-labeled complex [{Fe(CO)4 }(η2 -As2 D2 )] (2D) could be isolated. The electronic structure and bonding situation of 2 was elucidated by DFT calculations revealing that 2 is best described as an olefin-like complex. Moreover, the reactivity of 2 towards the Lewis acids [{M(CO)5 }(thf)] (M=Cr, W) was investigated, leading to the complexes [Fe(CO)4 AsHW(CO)5 ]2 (3) and [{Fe(CO)4 }2 AsH{Cr(CO)5 }] (4), respectively.

Directing energy transfer in Pt(bodipy)(mercaptopyrene) dyads.

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. σ-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-transfer from the electron-rich mercaptopyrene to the electron-accepting BDP ligand (PB-CT) gives rise to a multitude of (potentially) emissive states. This culminates in the presence of four different emissions for the mono- and dinuclear complexes BPtSPyr and BPtSPyrSPtB with an unsubstituted BDP ligand and either a terminal 1-mercaptopyrene or a bridging pyrene-1,6-dithiolate ligand. Thus, in fluid solution, near IR emission at 724 nm from the 3PB-CT state is observed with a quantum yield of up to 15%. Excitation into the BDP-based 1ππ* or the pyrene-based 1ππ* band additionally trigger fluorescence and phosphorescence emissions from the BDP-centred 1ππ* and 3ππ* states. In frozen solution, at 77 K, phosphorescence from the pyrene ligand becomes the prominent emission channel, while PB-CT emission is absent. Alkylation of the BDP ligand in KBPtSPyr funnels all excitation energy into fluorescence and phosphorescence emissions from the KBDP ligand. The assignments of the various excited states and the deactivation cascades were probed by absorption and emission spectroscopy, transient absorption spectroscopy, electrochemical and UV/Vis/NIR spectroelectrochemical measurements, and by quantum chemical calculations. Our conclusions are further corroborated with the aid of suitable reference compounds comprising of just one chromophore. All dyads are triplet sensitizers and are able to generate singlet oxygen.

Gold(I) Complexes Containing Phosphanyl- and Arsanylborane Ligands.

The structural and photophysical properties of a series of new AuI compounds have been studied. The reactions of AuCl(tht) with the phosphanyl- and arsanylboranes RR' EBH2 NMe3 (E=P, As; R=H, Ph; R'=H, Ph, tBu) afford the complexes [AuCl(RR' EBH2 NMe3 )]. In the solid state, [AuCl(H2 PBH2 NMe3 )]2 (2 a) is a dimer showing unsupported intermolecular aurophilic interactions with short Au⋅⋅⋅Au distances. In contrast, [AuCl(H2 AsBH2 NMe3 )]n (2 b) aggregates to form 1D chains. Organic substituents on the pnictogen atoms lead to discrete molecules in [AuCl(RR' PBH2 NMe3 )] (2 c: R=H, R'=tBu; 2 d: R=R'=Ph). To increase the aurophilicity, the ionic homoleptic complexes [Au(RR' EBH2 NMe3 )2 ][AlCl4 ] (3 a-d) have been synthesized, for which 3 a,b form chains in the solid state and exhibit luminescence. The emissions show a drastic redshift with temperature decrease, correlating with decreasing Au⋅⋅⋅Au distances. DFT calculations provide insight into the bonding situation of the products.

Mono- and dinuclear tetraphosphabutadiene ferrate anions.

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 presence of P4. Protonation of 3 affords [Na(THF)3][(CpArFe)2(µ,η4:4-P4)(H)] (4), while the reaction of 3 with trimethylchlorosilane gives the nortricyclane compound P7(SiMe3)3 as the main product.

Depolymerization of Poly(phosphinoboranes): From Polymers to Lewis Base Stabilized Monomers.

We report on depolymerization reactions of poly(phosphinoboranes). The cleavage of the polymers [H2 PBH2 ]n (2 a), [tBuHPBH2 ]n (2 c), [PhHPBH2 ]n (2 e) and the oligomer [Ph2 PBH2 ]n (2 b), with strong Lewis bases (LBs), in particular with NHCs, leads to the corresponding monomeric phosphanylboranes R1 R2 PBH2 LB. It is observed that the depolymerization depends on the strength and stability of the LBs as well as on the substitution pattern of the poly(phosphinoboranes). The solid state structures of the monomeric phosphinoboranes H2 PBH2 NHCMe (NHC=N-heterocyclic carbene) (4 a), H2 PBH2 NHCdipp (5 a) and tBuHPBH2 NHCMe (4 c) were determined. DFT calculations support the experimentally observed reaction behavior.

Macrocyclic Triruthenium Complexes Having Electronically Coupled Mixed-Valent States.

5-Ethynyl-2-furancarboxylic acid and 3-ethynylbenzoic acid self-assemble with [HRu(CO)Cl(PiPr3 )2 ] to form macrocyclic C3 -symmetric triangular triruthenium alkenyl complexes [{Ru(CO)(PiPr3 )2 (CH=CHArCOO)}3 ] (Ar=C6 H4 : 1-B, Ar=C4 H2 O: 1-F), which were characterized by multinuclear NMR spectroscopy, high-resolution ESI mass spectrometry, and, in the case of 1-B, by X-ray crystallography. Electrochemical studies indicate that the macrocycles are oxidized in three consecutive one-electron steps. The mixed-valent states obtained by electrochemical or chemical oxidation show signs of valence delocalization, which makes these complexes rare examples of molecule-based conductive loops with through-bond charge delocalization.