Thermolysis of Cs9MO4 (M = In, Sc): Synthesis, Crystal Structure, Chemical Bonding, and Reactivity of the Subvalent Oxidometalates Cs7MO4 (M = In, Sc).

The cesium-poor alkali-metal suboxidometalates Cs7MO4 (M = In, Sc) were prepared from the respective cesium-rich suboxidometalates Cs9MO4 by thermolysis in a dynamic vacuum at temperatures below 150 °C. They crystallize in a new structure type, comprising isolated tetrahedral oxidometalate anions [MO4]5- immersed in a matrix of metallic cesium atoms. This structural separation into alternating ionic and metallic building units is typical for subvalent compounds. Cs7InO4 and Cs7ScO4 are isotypic and form mixed crystals Cs7(In1-xScx)O4 with statistic distribution of In and Sc atoms. All compounds were characterized by single crystal and powder X-ray diffraction. Calculations of the electronic structure with DFT methods corroborate the coexistence of anionic entities within a metallic matrix and give evidence of the subvalent nature of cesium atoms. Overall metallic behavior is a consequence of the equal volume fractions of metallic and ionic regions, allowing for percolation of the conduction electrons throughout the crystal volume. Differential thermoanalysis was employed to gain insight into the chemical conversion processes during the thermolysis reaction. The thermolytic decomposition of Cs9MO4 is a multistep process with, in some instances, reversible amorphization and recrystallization steps. Finally, the formation of ionic compounds is observed. The full decomposition of Cs9ScO4 yields the two new oxidoscandates Cs14Sc4O13 and Cs17Sc5O15 with tetrahedral [ScO4] units connected to chain fragments and the indium compound yields cesium oxidoindates with low-condensed [InO4] building units. The cesium-poor suboxidometalates Cs7MO4 themselves can serve as starting materials for the synthesis of further, new suboxidometalates, as they show a unique reactivity toward metals.

Rotational conformers and nuclear spin isomers of carbonyl diisothiocyanate.

Nuclear spin isomers of molecules play a pivotal role in our understanding of quantum mechanics and can have significant implications for various fields. In this work, we report the isolation and characterization of stable nuclear spin isomers as well as conformational isomers of a reactive compound, namely carbonyl diisothiocyanate. It can exist as three rotational conformers, two of which, the syn-syn and syn-anti, were observed in a pulsed supersonic jet by chirped pulse Fourier transform microwave spectroscopy in the 2-12 GHz frequency region. The rotational spectra of two distinct nuclear spin isomers of syn-syn-carbonyl diisothiocyanate, ortho and para, were recorded and analyzed. Experimental molecular rotational parameters for the identified rotational and nuclear spin isomers were determined, including rotational constants, centrifugal distortion constants, and nuclear quadrupole coupling constants. The two nuclear spin isomers are distinguished by unique hyperfine splitting signatures in their rotational spectra as an outcome of their different nuclear spin states. The relative abundances of the two observed conformers in the gas phase were estimated from the intensity of their rotational transitions. Following detection of singly substituted rare isotopologues of the syn-syn conformer, a partial substitution (rs) structure was determined.

A comprehensive characterization of thiophosgene in the solid state.

Thiophosgene is one of the principal C=S building blocks in synthetic chemistry. At room temperature, thiophosgene is a red liquid. While its properties in the liquid and gaseous states are well known, a comprehensive characterization of thiophosgene in its solid state is presented here. Differential scanning calorimetry shows that thiophosgene forms a supercooled melt before rapidly crystallizing. Its melting point is 231.85 K (-41.3 °C). At 80 K, thiophosgene crystallizes in space group P63/m [No. 174, a = b = 5.9645 (2), c = 6.2835 (3) Å, V = 193.59 (2) Å3]. The molecule shows a distinct rotational disorder: all S and Cl positions are of mixed occupancy and the disorder does not resolve at temperatures as low as 10 K, as was shown by neutron powder diffraction. Infrared, Raman and inelastic neutron scattering spectra were collected and assigned with the aid of quantum chemical calculations. A larger ordered structural model allowed for better agreement between the measured and calculated spectra, further indicating that disorder is an inherent feature of solid-state thiophosgene.

Thiocarbonyl Pseudohalides - The Curious Case of Thiocarbonyl Dithiocyanate.

Thiocarbonyl dithiocyanate (1) and chlorothiocarbonyl thiocyanate (2) were synthesized from thiophosgene and ammonium or silver thiocyanate, respectivley. Their crystal structures show syn-anti (1) and syn (2) conformations, which were confirmed in the bulk phases by powder X-ray diffraction, vibrational spectroscopy and DFT calculations. Further calculations explain the isolation of the kinetic reaction products by a lower transition states opposed to the thermodynamic reaction products. Reaction of 1 with ethanol gave a dithiobiuret derivative (3). In a proof-of-principle study we show that it in turn can be used for the complexation of nickel to yield (4).

Cyclic Hydrocarbon Frameworks Containing Two Bismuth Atoms: Towards 9,10-Dibismaanthracene.

When bismuth atoms are incorporated into cyclic organic systems, this commonly goes along with strained or distorted molecular geometries, which can be exploited to modulate the physical and chemical properties of these compounds. In six-membered heterocycles, bismuth atoms are often accompanied by oxygen, sulfur or nitrogen as a second hetero-element. In this work, we present the first examples of six-membered rings, in which two CH units are replaced by BiX moieties (X=Cl, Br, I), resulting in dihydro-anthracene analogs. Their behavior in chemically reversible reduction reactions is explored, aiming at the generation of dibisma-anthracene (bismanthrene). Heterometallic compounds (Bi/Fe, Bi/Mn) are introduced as potential bismanthrene surrogates, as supported by bismanthrene-transfer to selenium. Analytical techniques used to investigate the reported compounds include NMR spectroscopy, high-resolution mass spectrometry, single-crystal X-ray diffraction analyses, and DFT calculations.

Synthesis and Stability of Ammonium Selenocyanate [NH4][SeCN] and Its Reactivity toward Ag[SeCN].

[NH4][SeCN] and Ag[SeCN] were synthesized by salt metathesis starting from the respective chlorides and K[SeCN]. Both products were fully characterized by single-crystal and powder X-ray diffraction, differential scanning calorimetry-thermogravimetric analysis (DSC-TGA), and solid-state IR and Raman spectroscopy. Quantum-mechanical calculations allowed for detailed assignment and interpretation of vibrational spectra. For dissolved [NH4][SeCN], nuclear magnetic resonance spectra were collected. High-temperature powder X-ray diffraction (HT-PXRD) allowed for the analysis of the thermal behavior of solid [NH4][SeCN]. Furthermore, the reaction of [NH4][SeCN] with Ag[SeCN] leads to the formation of the ternary salts [NH4][Ag(SeCN)2] and [NH4]3[Ag(SeCN)4]. The structures of the latter were determined from single-crystal X-ray diffraction (SC-XRD) data, and bulk analysis was performed by Rietveld refinement, Raman spectroscopy, and elemental analysis.

Expanding the Utility of ß-Diketiminate Ligands in Heavy Group VI Chemistry of Molybdenum and Tungsten.

We report the synthesis of 17 molybdenum and tungsten complexes supported by the ubiquitous BDI ligand framework (BDI = ß-diketiminate). The focal entry point is the synthesis of four molybdenum and tungsten(V) BDI complexes of the general formula [MO(BDIR)Cl2] [M = Mo, R = Dipp (1); M = W, R = Dipp (2); M = Mo, R = Mes (3); M = W, R = Mes (4)] synthesized by the reaction between MoOCl3(THF)2 or WOCl3(THF)2 and LiBDIR. Reactivity studies show that the BDIDipp complexes are excellent precursors toward adduct formation, reacting smoothly with dimethylaminopyridine (DMAP) and triethylphosphine oxide (OPEt3). No reaction with small phosphines has been observed, strongly contrasting the chemistry of previously reported rhenium(V) complexes. Additionally, the complexes 1 and 2 are good precursors for salt metathesis reactions. While 1 can be chemically reduced to the first stable example of a Mo(IV) BDI complex 15, reduction of 2 resulted in degradation of the BDI ligand via a nitrene transfer reaction, leading to MAD (4-((2,6-diisopropylphenyl)imino)pent-2-enide) supported tungsten(V) and tungsten(VI) complexes 16 and 17. All reported complexes have been thoroughly studied by VT-NMR and (heteronuclear) NMR spectroscopy, as well as UV-vis and EPR spectroscopy, IR spectroscopy, and X-ray diffraction analysis.

Double Addition vs. Ring Closure: Systematic Reactivity Study of CO(NCO)2 and CO(NCS)2 towards Hydrogen Halides.

The reactivity of carbonyl diisocyanate, CO(NCO)2 , and carbonyl diisothiocyanate, CO(NCS)2 with nucleophiles shows different patterns: Whereas carbonyl diisocyanate adds two equivalents of nucleophile forming carbonyl bis(carbamoylhalides), carbonyl diisothiocyanate only adds one equivalent and undergoes intramolecular ring closure, resulting in the formation of substituted thiadiazines. In this study we have reacted both carbonyl diisocyanate and carbonyl diisothiocyanate with the full series of hydrogen halides HF to HI, isolating carbonyl bis(carbamoylfluoride) (1), -chloride (2), -bromide (3), and -iodide (4) as well as (6-chloro-2,3-dihydro-2-thioxo-4H-1,3,5-thiadiazin-4-one (5), and 6-bromo-2,3-dihydro-2-thioxo-4H-1,3,5-thiadiazin-4-one (6). The compounds were analysed by single-crystal X-ray diffraction, NMR spectroscopy, IR and Raman spectroscopy, and elemental analysis. Quantum mechanical calculations show thermodynamic reasons for the differences in reactivity.

A Crystallographic, Spectroscopic, and Computational Investigation of Carbonyl and Oxalyl Diisothiocyanate.

Carbonyl diisothiocyanate (1) and oxalyl diisothiocyanate (2) were synthesized by reactions of phosgene and oxalyl chloride with ammonium thiocyanate, respectively. Their structures were elucidated by single-crystal X-ray diffraction. 1 exhibits weak intermolecular S-O contacts forming a loosely connected network of molecules, whereas 2 exhibits weak intermolecular Ccarbonyl-O contacts resulting in the formation of layers. Both compounds were further characterized by nuclear magnetic resonance, infrared, and Raman spectroscopy. Quantum-chemical calculations reproduced the experimental structures and enabled the interpretation of the vibrational spectra.

Homoleptic quasilinear metal(i/ii) silylamides of Cr-Co with phenyl and allyl functions - impact of the oxidation state on secondary ligand interactions.

Herein we describe the synthesis and characterization of a variety of new quasilinear metal(i/ii) silylamides of the type [M(N(Dipp)SiR3)2]0,- (M = Cr-Co) with different silyl substituents (SiR3 = SiPh3-nMen (n = 1-3), SiMe2(allyl)). By comparison of the solid state structures we show that in the case of phenyl substituents secondary metal-ligand interactions are suppressed upon reduction of the metal. Introduction of an allyl substituted silylamide gives divalent complexes with additional metal-π-alkene interactions with only weak activation of the C[double bond, length as m-dash]C bond but substantial bending of the principal N-M-N axis. 1e--reduction makes cobalt a more strongly bound alkene substituent, whereas for chromium, reduction and intermolecular dimerisation of the allyl unit are observed. It thus indicates that the general view of low-coordinate 3d-metal ions as electron deficient seems not to apply to anionic metal(i) complexes. Additionally, the obtained cobalt(i) complexes are reacted with an aryl azide giving trigonal imido metal complexes. These can be regarded as rare examples of high-spin imido cobalt compounds from their structural and solution magnetic features.

A Comprehensive Study on the Full Series of Alkali-Metal Selenocyanates AI [SeCN] (AI =Li-Cs).

The full series of quasibinary alkali-metal selenocyanates was synthesized either by oxidation of the respective cyanides (A=Li-Rb) or by metathesis (A=Cs). For Li[SeCN] only ball-milling and subsequent annealing led to the isolation of the quasibinary selenocyanate. Their structures were refined from single-crystal and powder X-ray data. The respective solid-state IR and Raman spectra were interpreted with the aid of solid-state quantum-mechanical calculations and DSC-TGA measurements allowed for extraction of melting points. Only for Li[SeCN] a possible phase transition was observed that is discussed on the basis of VT-PXRD experiments. It is also the only quasibinary selenocyanate to form a hydrate (Li[SeCN] ⋅ 2H2 O).

Insights into Formation and Relationship of Multimetallic Clusters: On the Way toward Bi-Rich Nanostructures.

Bismuth-rich polyanions show a unique potential in constructing nanostructured bismuth-based materials, but they are still poorly investigated. We use a ternary precursor of the nominal composition "K5Ga2Bi4" for the formation of [K(crypt-222)]+ salts of novel Bi-rich polyanions [Bi@Ga8(Bi2)6]q- (q = 3, 5; in 1), (Ga2Bi16)4- (in 2), and [{Ru(cod)}4Bi18]4- (in 3). Their bismuth contents exceed that of the largest homoatomic polyanion, Bi113-. The numbers of bismuth atoms in the anions in 2 and 3 furthermore surmount that of the Bi-richest binary main-group anion, (Ge4Bi14)4-, and they equal (2) or surmount (3) that reported for the anion and the cations with the largest number of Bi atoms so far, [K2Zn20Bi16]6-, [(Bi8)Ru(Bi8)]6+, and [(Bi8)Au(Bi8)]5+. Compounds 1 and 2 were obtained from reaction mixtures that contain [La(C5Me4H)3], apparently assisting in the network formation without being included in the products. In the presence of [Ru(cod)(H2CC(Me)CH2)2], yet another reaction pathway leads to the formation of the anions in 3 (conformers 3a and 3b), which are Bi-Bi linked dimers of two "[{Ru(cod)}2Bi9]2-" subunits. They comprise the largest connected assemblies of Bi atoms within one molecule and may be viewed as snapshots on the way toward even larger polybismuthide units and, ultimately, new bismuth modifications. Mass spectrometry allowed insight into the processes in solution that precede the cluster formation. In-depth quantum chemical studies were applied to explain structural peculiarities, stabilities of the observed isomers, and bonding characteristics of these bismuth-rich nanoarchitectures. The work demonstrates the high potential of the method for the access of new Bi-based materials.

η3 -Coordination and Functionalization of the 2-Phosphaethynthiolate Anion at Lanthanum(III)*.

We present the η3 -coordination of the 2-phosphaethynthiolate anion in the complex (PN)2 La(SCP) (2) [PN=N-(2-(diisopropylphosphanyl)-4-methylphenyl)-2,4,6-trimethylanilide)]. Structural comparison with dinuclear thiocyanate-bridged (PN)2 La(µ-1,3-SCN)2 La(PN)2 (3) and azide-bridged (PN)2 La(µ-1,3-N3 )2 La(PN)2 (4) complexes indicates that the [SCP]- coordination mode is mainly governed by electronic, rather than steric factors. Quantum mechanical investigations reveal large contributions of the antibonding π*-orbital of the [SCP]- ligand to the LUMO of complex 2, rendering it the ideal precursor for the first functionalization of the [SCP]- anion. Complex 2 was therefore reacted with CAACs which induced a selective rearrangement of the [SCP]- ligand to form the first CAAC stabilized group 15-group 16 fulminate-type complexes (PN)2 La{SPC(R CAAC)} (5 a,b, R=Ad, Me). A detailed reaction mechanism for the SCP-to-SPC isomerization is proposed based on DFT calculations.

Ionic Liquid-Driven Formation of and Cation Exchange in Layered Sulfido Stannates - a CH2 Group Makes the Difference.

Two types of layered sulfido stannates or a molecular cluster compound are obtained upon ionothermal treatment of the simple sulfido stannate salt K4 [SnS4 ] · 4H2 O that is based on binary tetrahedral [SnS4 ]4- anions. The formation of the respective products, novel compounds (C4 C1 C1 Im)2 [Sn3 S7 ] (1 a), (C4 C1 C2 Im)2 [Sn3 S7 ] (1 b), and (C4 C1 C2 Im)2 [Sn4 S9 ] (2) with layered anionic substructures, or the recently reported compound (C4 C1 C1 Im)4+x [Sn10 O4 S16 (SMe)4 ][An]x (A) comprising a molecular cluster anion, is controlled by both the choice of the ionic liquid cation and the reaction temperature. We report the scale-up of the syntheses by a factor of 100 with regard to other reported ionothermal syntheses of related compounds, and a procedure of how to isolate them in phase-pure form - both being rare observations in chalcogenido stannate chemistry in ionic liquids. Moreover, the synthesis of compound 1 a can be achieved by rapid cation exchange starting out from 1 b, which has not been reported for organic cations in any chalcogenido stannate salt to date.

Trapping of ZnCl2 by bipyridyl-functionalized organotin sulfide clusters, and its effect on optical properties.

We report the syntheses of two new organotin sulfide clusters with heteroaromatic substituents. A phenanthroline-functionalized tin sulfide cluster [(RPhenSn)4S6] (1; RPhen = CMe2CH2C(Me)N-NC(H)C12H7N2) and a bipyridyl-terminated cluster [(R4-bipySn)4S6] (2; R4-bipy = CMe2CH2C(Me)N-NC(H)-4-C10H7N2) were obtained from reactions of the hydrazone-functionalized organotin sulfide cluster [(RNSn)4S6] (RN = CMe2CH2C(Me)N-NH2) with 1,10-phenanthroline-5-carboxaldehyde or 2,2'-bipyridine-4-carbaldehyde. 1 and 2 were tested towards their capability of trapping metal ions by means of the terminal chelating ligands. The reaction of 2 with ZnCl2 afforded the cluster compound [(R4-bipyZnCl2Sn)4S6] (5), in which four ZnCl2 units are coordinated by the heteroaromatic organic groups. We discuss the structures and demonstrate the effect of ZnCl2 trapping on optical absorption and luminescence properties.

Photoelectron Spectroscopy and Theoretical Studies of PCSe- , AsCS- , AsCSe- , and NCSe- : Insights into the Electronic Structures of the Whole Family of ECX- Anions (E=N, P, As; X=O, S, Se).

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 affinities (EA), spin-orbit (SO) splittings, and "symmetric"/"asymmetric" stretching frequencies of the neutral radicals ECX. (E=N, P, As; X=S, Se), generated by electron detachment from the corresponding anions, were obtained from the spectra. The calculated EAs, SO splittings, and vibrational frequencies are in excellent agreement with the experimental measurements. These newly obtained values, when combined with those previously determined for the lighter analogues, show interesting trends on descending the pnictogen and chalcogen series. These trends are rationalized based on electronegativity arguments, the electron distributions in the HOMOs, and NBO/NRT analyses.

A General Synthesis of Phosphorus- and Arsenic-Containing Analogues of the Thio- and Seleno-cyanate Anions.

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 structures, electronic properties, and spectroscopic signatures of these species are reported.

Electrocrystallization: A Synthetic Method for Intermetallic Phases with Polar Metal-Metal Bonding.

Isothermal electrolysis is a convenient preparation technique for a large number of intermetallic phases. A solution of the salt of a less-noble metal is electrolyzed on a cathode consisting of a liquid metal or intermetallic system. This yields crystalline products at mild reaction conditions in a few hours. We show the aptness and the limitations of this approach. First, we give an introduction into the relevance of electrolytic synthesis for chemistry. Then we present materials and techniques our group has developed for electrocrystallization that are useful for electrochemical syntheses in general. Subsequently, we discuss different phase formation eventualities and propose basic rationalization concepts, illustrated with examples from our work. The scope of this report is to present electrocrystallization as a well-known yet underestimated synthetic process, especially in intermetallic chemistry. For this purpose we adduce literature examples (Li3Ga14, NaGa4, K8Ga8Sn38), technical advice, basic concepts, and new crystal structures only available by this method: Li3Ga13Sn and CsIn12. Electrocrystallization has recently proven especially helpful in our work concerning synthesis of intermetallic phases with polar metal-metal bonding, especially Hg-rich amalgams of less-noble metals. With the term "polar metal-metal bonding" we describe phases where the constituting elements have large electronegativity difference and yet show incomplete electron transfer from the less-noble to the nobler metal. This distinguishes polar intermetallic phases from classical Zintl phases where the electron transfer is virtually complete. Polar metallic phases can show "bad metal behavior" and interesting combinations of ionic and metallic properties. Amalgams of less-noble metals are preeminent representatives for this class of intermetallic phases as Hg is the only noble metal with endothermic electron affinity and thus a very low tendency toward anion formation. To illustrate both the aptness of the electrocrystallization process and our interest in polar metals in the above-mentioned sense, we present amalgams but also Hg-free intermetallics.

Chemical Twinning of Salt and Metal in the Subnitridometalates Ba23 Na11 (MN4 )4 with M=V, Nb, Ta.

The subnitridometalates Ba23 Na11 (MN4 )4 (M=V, Nb, Ta) crystallize in a new structure type, which shows ionic ortho-nitridometalate anions and motifs from simple (inter)metallic packings: Na-centered [Na8 ] cubes as cutouts of the bcc structure of elemental Na and Na-centered [Ba10 Na2 ] icosahedra as found in Laves phases, for example. Single-crystal and powder X-ray diffraction studies in combination with quantum-chemical calculations of the electronic structure and Raman spectroscopy support the characterization of the subnitridometalates as "chemical twins". They consist of independent building units with locally prevalent ionic or metallic bonding in an overall metallic compound.

Redetermination of [EuCl2(H2O)6]Cl.

The crystal structure of the title compound, hexa-aqua-dichlorido-europium(III) chloride, was redetermined with modern crystallographic methods. In comparison with the previous study [Lepert et al. (1983 ▶). Aust. J. Chem. 36, 477-482], it could be shown that the atomic coordinates of some O atoms had been confused and now were corrected. Moreover, it was possible to freely refine the positions of the H atoms and thus to improve the accurracy of the crystal structure. [EuCl2(H2O)6]Cl crystallizes with the GdCl3·6H2O structure-type, exhibiting discrete [EuCl2(H2O)6](+) cations as the main building blocks. The main blocks are linked with isolated chloride anions via O-H⋯Cl hydrogen bonds into a three-dimensional framework. The Eu(3+) cation is located on a twofold rotation axis and is coordinated in the form of a Cl2O6 square anti-prism. One chloride anion coordinates directly to Eu(3+), whereas the other chloride anion, situated on a twofold rotation axis, is hydrogen bonded to six octa-hedrally arranged water mol-ecules.