Scalable Bulk Synthesis of Phase-Pure γ-SnN as a Model for an Argon-Flow-Mediated Metathesis Reaction.

Nitrides represent a promising class of materials for a variety of applications. However, bulk synthesis remains a challenging task due to the stability of the N molecule. In this study, we introduce a simple and scalable approach for synthesizing nitride bulk materials.

Reduction of Germanium Oxides-The Mixed-Valence Germanates GeO ( = Na, K).

We report on the synthesis of two-layered alkali germanates, NaGeO and KGeO. Both compounds were synthesized by using the ammonothermal method at 823 K and 100 MPa. Under these conditions, germanium is partially reduced from the +IV state to +II, forming mixed-valence compounds with the rarely observed [GeO] unit.

Reactions of [SiF(NH)] with Fluorides AF (A = Li-Cs, Tl, NH) in Liquid NH: A [NH(NH)] Cation and a Thallophilic Interaction in [Tl(NH)].

We investigated whether [SiF(NH)] can act as a fluoride-ion acceptor in its reactions with the fluorides F ( = Li-Cs, Tl, NH) in anhydrous liquid ammonia (NH). While LiF and NaF did not react, we obtained the compounds K[SiF(NH)], Rb[SiF(NH)], and Cs[SiF(NH)], as well as [NH(NH)][SiF] and [Tl(NH)][SiF]·2NH, from the other starting materials and characterized them by either single-crystal or powder X-ray diffraction. The compound [NH(NH)][SiF] contains the very rarely observed hydrogen-bonded, -symmetric diammine ammonium cation [NH(NH)], and the compound [Tl(NH)][SiF]·2NH is an example for an uncommon Tl(I)-Tl(I) interaction.

Complexes featuring a linear [N≡U≡N] core isoelectronic to the uranyl cation.

The aqueous chemistry of uranium is dominated by the linear uranyl cation [UO], yet the isoelectronic nitrogen-based analogue of this ubiquitous cation, molecular [UN], has so far only been observed in an argon matrix. Here, we present three different complexes of [UN] obtained by the reaction of the uranium pentahalides UCl or UBr with anhydrous liquid ammonia. The [UN] moieties are linear, with the U atoms coordinated by five additional ligands (ammonia, chloride or bromide), resulting in a pentagonal bipyramidal coordination sphere that is also commonly adopted by the uranyl cation [UO(L)] (L, ligand).

A Revised Structure Model for the UCl Structure Type, Novel Modifications of UCl and UBr , and a Comment on the Modifications of Protactinium Pentabromides.

The redetermination of the crystal structure of trigonal UCl , which is the eponym for the UCl structure type, showed that certain atomic coordinates had been incorrectly reported. This led to noticeably different U-Cl distances within the octahedral UCl molecule (2.41 and 2.

Formation and Properties of the Trichloroberyllate Ion.

The activation of C-Cl bonds in dichloromethane and chloroform was observed by BeCl in the presence of PMe and PCy. This leads to the formation of [MePCHCl]Cl and [CyPCHCl][BeCl]. The latter compound is the first example of a tricoordinated beryllium species with nonbulky ligands and proof of the existence and stability of the long-predicted [BeCl] ion.

Nanosized Gadolinium and Uranium-Two Representatives of High-Reactivity Lanthanide and Actinide Metal Nanoparticles.

Gadolinium (Gd) and uranium (U) nanoparticles are prepared via lithium naphthalenide ([LiNaph])-driven reduction in tetrahydrofuran (THF) using GdCl and UCl, respectively, as low-cost starting materials. The as-prepared Gd and U suspensions are colloidally stable and contain metal nanoparticles with diameters of 2.5 ± 0.

Crown Ether Complexes of Alkali-Metal Chlorides from SO.

The structures of alkali-metal chloride SO solvates (Li-Cs) in conjunction with 12-crown-4 or 1,2-disila-12-crown-4 show strong discrepancies, despite the structural similarity of the ligands. Both types of crown ethers form 1:1 complexes with LiCl to give [Li(1,2-disila-12-crown-4)(SO Cl)] (1) and [Li(12-crown-4)Cl]⋅4 SO (2). However, 1,2-disila-12-crown-4 proved unable to coordinate cations too large for the cavity diameter, for example, by the formation of sandwich-type complexes.

Facile syntheses of pure uranium halides: UCl, UBr and UI.

Herein we describe convenient lab scale syntheses of several uranium(iv) halides of high purity by reaction of AlX (X = Cl, Br and I) with UO, which is readily available by reduction of uranyl salts like UO(NO)·6HO. UCl, UBr, and UI are obtained in the form of aggregates of large single crystals. Their identities and purity were checked by powder X-ray diffraction, IR spectroscopy and elemental analysis.

Beryllium Phosphine Complexes: Synthesis, Properties, and Reactivity of (PMe ) BeCl and (Ph PC H PPh )BeCl.

The directed synthesis, spectroscopic properties, and reactivity of bis(trimethylphosphine) beryllium dichloride (1) and bis(diphenylphosphino)propane beryllium dichloride (2) are reported, including the crystal structure of (PMe ) BeCl (1). These four-coordinate beryllium compounds can be alkylated with n-butyllithium ( BuLi) to give three-coordinate (Ph PC H PPh )Be Bu (3) and (PMe )Be Bu (4). PMe can be removed from (PMe )Be Bu (4) in vacuo to yield [ Bu Be] (5).

A 1D Coordination Polymer of UF with HCN as a Ligand.

β-Uranium(V) fluoride was reacted with liquid anhydrous hydrogen cyanide to obtain a 1D coordination polymer with the composition 1∞ [UF (HCN) ], 1∞ [UF F - (HCN) ], revealed by single-crystal X-ray structure determination. The reaction system was furthermore studied by means of vibrational and NMR spectroscopy, as well as by quantum chemical calculations. The compound presents the first described polymeric HCN Lewis adduct and the first HCN adduct of a uranium fluoride.

NOUF6 Revisited: A Comprehensive Study of a Hexafluoridouranate(V) Salt.

We have synthesized NOUF6 by direct reaction of NO with UF6 in anhydrous HF (aHF). Based on the unit cell volume and powder diffraction data, the compound was previously reported to be isotypic to O2 PtF6 , however, detailed structural data, such as the atom positions and all information that can be derived from those, were unavailable. We have therefore investigated the compound by using single-crystal and powder X-ray diffraction, IR, Raman, NMR, EPR, and photoluminescence spectroscopy, magnetic measurements, as well as chemical analysis, density determination, and quantum chemical calculations.