Reactivity of Liquid Ammonia Solutions of the Zintl Phase K12Sn17 towards Mesitylcopper(I) and Phosphinegold(I) Chloride

To gain more insight into the reactivity of intermetalloid clusters, the reactivity of the Zintl phase K₁₂Sn₁₇, which contains [Sn₄]^4? and [Sn₉]^4? cluster anions, was investigated. The reaction of K₁₂Sn₁₇ with gold(I) phosphine chloride yielded K₇[(η²‐Sn₄)Au(η²‐Sn₄)](NH₃)₁₆ ( 1 ) and K₁₇[(η²‐Sn₄)Au(η²‐Sn₄)]₂(NH₂)₃(NH₃)₅₂ ( 2 ), which both contain the anion [(Sn₄)Au(Sn₄)]^7? ( 1 a ) that consists of two [Sn₄]^4? tetrahedra linked through a central gold atom. Anion 1 a represents the first binary Au?Sn polyanion. From this reaction, the solvate structure [K([2.2.2]crypt)]₃K[Sn₉](NH₃)₁₈ ( 3 ; [2.2.2]crypt=4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane) was also obtained. In the analogous reaction of mesitylcopper with K₁₂Sn₁₇ in the presence of [18]crown‐6 in liquid ammonia, crystals of the composition [K([18]crown‐6)]₂[K([18]crown‐6)(MesH)(NH₃)][Cu@Sn₉](thf) ( 4 ) were isolated ([18]crown‐6=1,4,7,10,13,16‐hexaoxacyclooctadiene, MesH=mesitylene, thf=tetrahydrofuran) and featured a [Cu@Sn₉]^3? cluster. A similar reaction with [2.2.2]crypt as a sequestering agent led to the formation of crystals of [K[2.2.2]crypt][MesCuMes] ( 5 ). The cocrystallization of mesitylene in 4 and the presence of [MesCuMes]^? ( 5 a ) in 5 provides strong evidence that the migration of a bare Cu atom into an Sn₉ anion takes place through the release of a Mes^? anion from mesitylcopper, which either migrates to another mesitylcopper to form 5 a or is subsequently protonated to give MesH.     

Synthesis,Structural, and Optical Characterization of a New Europium(II) Tin Selenide,Eu8(Sn4Se14)(Se3)2 with a (Sn4Se14)12– Building Block

A new phase in europium‐tin‐chalcogenide chemistry has been prepared using the reactive flux method: Eu₈(Sn₄Se₁₄)(Se₃)₂. The compound crystallizes in the orthorhombic space group P2₁2₁2 with cell parameters a = 11.990(2) Å, b = 16.425(4) Å, c = 8.543(1) Å, and Z = 2. Eu₈(Sn₄Se₁₄)(Se₃)₂ is a three dimensional structure with Eu^II cations linked together with an unusual (Sn₄Se₁₄)^12– anionic unit and (Se₃)^2– chains. UV‐VIS‐NIR band‐gap analysis shows that these black metallic crystals are likely semiconductors with an optical band‐gap of 1.07 eV.     

On the Formation of Intermetalloid Clusters: Titanocene(III)diammin as a Versatile Reactant Toward Nonastannide Zintl Clusters

The reactivity of TiCp₂Cl₂ (d⁰) towards Zintl clusters was studied in liquid ammonia (Cp=cyclopentadienyl). Reduction of Ti^IVCp₂Cl₂ and ligand exchange led to the formation of [Ti^IIICp₂(NH₃)₂]⁺, also obtainable by recrystallization of [CpTi^IIICl]₂. Upon reaction with [K₄Sn₉], ligand exchange leads to [TiCp₂(η¹‐Sn₉)(NH₃)]^3?. A small variation of the stoichiometry led to the formation of [Ti(η⁴‐Sn₈)Cp]^3?, which cocrystallizes with [TiCp₂(NH₃)₂]⁺ and [TiCp₂(η¹‐Sn₉)(NH₃)]^3?. Finally, the large intermetalloid cluster anion [Ti₄Sn₁₅Cp₅]^n? (n=4 or 5) was obtained from the reaction of K₁₂Sn₁₇ and TiCp₂Cl₂ in liquid ammonia. The isolation of three side products, [K([18]crown‐6)]Cp, [K([18]crown‐6)]Cp(NH₃), and [K([2.2]crypt)]Cp, suggests a stepwise elimination of the Cl^? and Cp^? ligands from TiCp₂Cl₂ and thus gives a hint to the mechanism of the product formation in which [Ti(η⁴⁺²‐Sn₈)Cp]^3? has a key role.     

Theoretical Study of α‐V2O5‐Based Double‐Wall Nanotubes

First‐principles calculations of the atomic and electronic structure of double‐wall nanotubes (DWNTs) of α‐V₂O₅ are performed. Relaxation of the DWNT structure leads to the formation of two types of local regions: 1) bulk‐type regions and 2) puckering regions. Calculated total density of states (DOS) of DWNTs considerably differ from that of single‐wall nanotubes and the single layer, as well as from the DOS of the bulk and double layer. Small shoulders that appear on edges of valence and conduction bands result in a considerable decrease in the band gaps of the DWNTs (up to 1 eV relative to the single‐layer gaps). The main reason for this effect is the shift of the inner‐ and outer‐wall DOS in opposite directions on the energetic scale. The electron density corresponding to shoulders at the conduction‐band edges is localized on vanadium atoms of the bulk‐type regions, whereas the electron density corresponding to shoulders at the valence‐band edges belongs to oxygen atoms of both regions.     

[AuII([12]anS4)]2+ – X‐ und Q‐Band‐EPR‐spektroskopischer Nachweis einer neuen monomeren Gold(II)‐Verbindung

[Au^II([12]anS₄)]²⁺ – X‐ and Q‐Band EPR Evidence of a New Monomeric Gold(II) Compound The reaction of [Au^IIICl₄]^– with the thiacrown ether [12]aneS₄ leads to an instable [Au^II([12]anS₄)]²⁺ complex (5d⁹, S = 1/2) which was characterized by X‐ and Q‐ band EPR. The spin Hamiltonian parameters g , A ^Au and P ^Au were derived using a program package allowing an exact diagonalisation of the spin‐Hamiltonian‐Matrix. The EPR parameters suggest the coordination of only one thiacrown ether ligand in the new Au^II complex.     

Rationalization of the behavior of M2(CH3CS2)4I (M = Ni,Pt) chains at room temperature from periodic density functional theory and ab initio cluster calculations

The electrical conductivities and plausible charge‐ordering states in the room temperature (r.t.) phase for MMX chains [Ni₂(dta)₄I]_∞ and [Pt₂(dta)₄I]_∞ (dta = CH₃CS) have been analyzed with periodic density functional theory (DFT) and correlated ab initio calculations combined with the effective Hamiltonian theory. Periodic DFT calculations show a more delocalized nature of the ground state in [Pt₂(dta)₄I]_∞ compared to [Ni₂(dta)₄I]_∞, which features a rather large energy gap between the occupied and empty bands, and charge polarized dimer units. A larger electrical conductivity for the Pt chain can be expected, especially because the Fermi level lies within a band with contributions from Pt and I orbitals. Electronic structure parameters extracted from ab initio cluster calculations show that the large difference between the observed conductivities at 300 K for Ni and Pt compounds, of 3 orders of magnitude, cannot be explained from the parameters extracted from an embedded M₂(dta)₄I₂ dimer fragment alone. When tetramer fragments are considered, we observe that the interdimer transfer integral (t) between neighboring M₂ units connected by an iodine atom at correlated level is comparable in both chains. On the other hand, the energy to transfer an electron from a dimer to the neighboring one (Coulomb repulsion U) is three times larger in the Ni compound with respect to the Pt chain, in line with the poor conductivity of the former. The electronic structure of the M₄(dta)₈I₃ fragment points to an alternate charge‐polarization state for Ni and an average valence state for Pt when the r.t. X‐ray structure is considered. © 2012 Wiley Periodicals, Inc.     

Two‐Dimensional Haeckelite NbS2: A Diamagnetic High‐Mobility Semiconductor with Nb4+ Ions

In all known Group 5 transition‐metal dichalcogenide monolayers (MLs), the metal centers carry a spin, and their ground‐state phases are either metallic or semiconducting with indirect band gaps. Here, on grounds of first‐principles calculations, we report that the Haeckelite polytypes 1 S ‐NbX₂ (X=S, Se, Te) are diamagnetic direct‐band‐gap semiconductors even though the Nb atoms are in the 4+ oxidation state. In contrast, 1 S ‐VX₂ MLs are antiferromagnetically coupled indirect‐band‐gap semiconductors. The 1 S phases are thermodynamically and dynamically stable but of slightly higher energy than their 1 H and 1 T ML counterparts. 1 S ‐NbX₂ MLs are excellent candidates for optoelectronic applications owing to their small band gaps (between 0.5 and 1 eV). Moreover, 1 S ‐NbS₂ shows a particularly high hole mobility of 2.68×10³ cm² V⁻¹ s⁻¹, which is significantly higher than that of MoS₂ and comparable to that of WSe₂.     

Atomically Thin Arsenene and Antimonene: Semimetal–Semiconductor and Indirect–Direct Band‐Gap Transitions

The typical two‐dimensional (2D) semiconductors MoS₂, MoSe₂, WS₂, WSe₂ and black phosphorus have garnered tremendous interest for their unique electronic, optical, and chemical properties. However, all 2D semiconductors reported thus far feature band gaps that are smaller than 2.0 eV, which has greatly restricted their applications, especially in optoelectronic devices with photoresponse in the blue and UV range. Novel 2D mono‐elemental semiconductors, namely monolayered arsenene and antimonene, with wide band gaps and high stability were now developed based on first‐principles calculations. Interestingly, although As and Sb are typically semimetals in the bulk, they are transformed into indirect semiconductors with band gaps of 2.49 and 2.28 eV when thinned to one atomic layer. Significantly, under small biaxial strain, these materials were transformed from indirect into direct band‐gap semiconductors. Such dramatic changes in the electronic structure could pave the way for transistors with high on/off ratios, optoelectronic devices working under blue or UV light, and mechanical sensors based on new 2D crystals.     

Metalloradicals Supported by a meta‐Carborane Ligand

In this work, a pincer‐type complex [Cp*Ir‐(SNPh)(SNHPh)(C₂B₁₀H₉)] ( 2 ) was synthesized and its reactivity studied in detail. Interestingly, molecular hydrogen can induce the transformation between the metalloradical [Cp*Ir‐(SNPh)₂(C₂B₁₀H₉)] ( 5 ^.) and 2 . A mixed‐valence complex, [(Cp*Ir)₂‐(SNPh)₂(C₂B₁₀H₈)] ( 7 ^.+), was also synthesized by one‐electron oxidation. Studies show that 7 ^.+ is fully delocalized, possessing a four‐centered‐one‐electron (S‐Ir‐Ir‐S) bonding interaction. DFT calculations were also in good agreement with the experimental results.     

Poly[μ‐2‐aminopyrazine‐κ2N1:N4‐μ‐cyanido‐copper(I)]: a three‐dimensional network from laboratory powder diffraction data

In the title compound, [Cu(CN)(C₄H₅N₃)]_n or [Cu(μ‐CN)(μ‐PyzNH₂)]_n (PyzNH₂ is 2‐aminopyrazine), the Cu^I center is tetrahedrally coordinated by two cyanide and two PyzNH₂ ligands. The Cu^I–cyano links give rise to [Cu–CN]_∞ chains running along the c axis, which are bridged by bidentate PyzNH₂ ligands. The three‐dimensional framework can be described as being formed by two interpenetrated three‐dimensional honeycomb‐like networks, both made of 26‐membered rings of composition [Cu₆(μ‐CN)₂(μ‐PyzNH₂)₄].     

Thermally Induced Valence Tautomeric Transition in a Two‐Dimensional Fe‐Tetraoxolene Honeycomb Network

A novel tetraoxolene‐bridged Fe two‐dimensional honeycomb layered compound, (NPr₄)₂[Fe₂(Cl₂An)₃] ?2 (acetone)?H₂O ( 1 ), where Cl₂An^n?=2,5‐dichloro‐3,6‐dihydroxy‐1,4‐benzoquinonate and NPr₄⁺=tetrapropylammonium cation, has been synthesized. 1 revealed a thermally induced valence tautomeric transition at T_1/2=236 K (cooling)/237 K (heating) between Fe^m+ (m=2 or 3) and Cl₂An^n? (n=2 or 3) that induced valence modulations between [Fe^II_HSFe^III_HS(Cl₂An^2?)₂(Cl₂An^.3?)]^2? at T>T_1/2 and [Fe^III_HSFe^III_HS(Cl₂An^2?)(Cl₂An^.3?)₂]^2? at T<T_1/2. Even in a two‐dimensional network structure, the low‐temperature phase [Fe^III_HSFe^III_HS(Cl₂An^2?)(Cl₂An^.3?)₂]^2? valence set can be regarded as a magnetic chain‐knit network, where ferrimagnetic Δ and Λ chains of [Fe^III_HS(Cl₂An^.3?)]_∞ are alternately linked by the diamagnetic Cl₂An^2?. This results in a slow magnetization behavior attributed to the structure acting as a single‐chain magnet at lower temperatures.     

Copper(II) succinate complexes with 1,2‐di‐4‐pyridylethane and 1,3‐di‐4‐pyridylpropane

The compounds poly[di‐μ₄‐succinato‐μ₂‐1,2‐di‐4‐pyridylethane‐dicopper(II)], [Cu₂(C₄H₄O₄)₂(C₁₂H₁₂N₂)]_n, (I), and poly[di‐μ₄‐succinato‐μ₂‐1,3‐di‐4‐pyridylpropane‐dicopper(II)], [Cu₂(C₄H₄O₄)₂(C₁₃H₁₄N₂)]_n, (II), exhibit polymeric structures with the dicopper units doubly bridged by bis‐bidentate succinate groups and crosslinked by the separator bis(pyridyl) molecules. In (I), the molecule exhibits a centre of inversion located midway between the core Cu‐dimer atoms and another that relates half of the bis(pyridyl)ethane ligand to the other half. Compound (II) has a similar molecular packing but with a doubled lattice constant and noncentrosymmetric core units. An antiferromagnetic interaction due to the dinuclear copper units was deduced from magnetic subsceptibility measurements, and spin triplet signals were detected in the electron paramagnetic resonance spectra for both compounds.     

[ReF6]2−: A Robust Module for the Design of Molecule‐Based Magnetic Materials

A facile synthesis of the [ReF₆]^2? ion and its use as a building block to synthesize magnetic systems are reported. Using dc and ac magnetic susceptibility measurements, INS and EPR spectroscopies, the magnetic properties of the isolated [ReF₆]^2? unit in (PPh₄)₂[ReF₆]?2 H₂O ( 1 ) have been fully studied including the slow relaxation of the magnetization observed below ca. 4 K. This slow dynamic is preserved for the one‐dimensional coordination polymer [Zn(viz)₄(ReF₆)]_∞ ( 2 , viz=1‐vinylimidazole), demonstrating the irrelevance of low symmetry for such magnetization dynamics in systems with easy‐plane‐type anisotropy. The ability of fluoride to mediate significant exchange interactions is exemplified by the isostructural [Ni(viz)₄(ReF₆)]_∞ ( 3 ) analogue in which the ferromagnetic Ni^II–Re^IV interaction (+10.8 cm^?1) dwarfs the coupling present in related cyanide‐bridged systems. These results reveal [ReF₆]^2? to be an unique new module for the design of molecule‐based magnetic materials.     

Light Absorption Properties and Electronic Band Structures of Lead‐Vanadium Oxyhalide Apatites Pb5(VO4)3X (X=F,Cl, Br,I)

The Pb‐V oxyhalide apatite compounds Pb₅(VO₄)₃X (X=F, Cl, Br, I) were successfully synthesized using a facile solution method and studied with respect to their structural/optical characteristics and electronic band structures. UV‐visible diffuse reflectance spectroscopy, electrochemical analysis and first‐principles calculations showed that the synthesized apatites behaved as n‐type semiconductors, with absorption bands in the UV‐visible region that could be assigned to electron transitions from the valence band to a conduction band formed by hybridized V 3d and Pb 6p orbitals. Among the apatites examined, Pb₅(VO₄)₃I had the smallest band gap of 2.7 eV, due to an obvious contribution of I 5p orbitals to the valence band maximum. Based on its visible light absorption capability, Pb₅(VO₄)₃I generated a continuous anodic photocurrent under visible light (λ>420 nm) in a solution of 0.1 m NaI in acetonitrile.     

Silver clusters in the cages of zeolites: A quantum chemical study

The electronic structure of zeolite A is developed in a step by step procedure from the simple O_hH₈Si₈O₁₂ molecule, to the _∞ ¹ [(-O)₂H₄[Si₈O₁₂)] chain, to the _∞ ² [(-O₄)(Si₈O₁₂)] layer, and finally to the silica zeolite A framework _∞ ³ [Si₂₄O₄₈]. It is remarkable how well the calculated band structures of both, _∞ ² [(-O)₄(Si₈O₁₂)] and _∞ ³ [Si₂₄O₄₈] correspond to the experimentally determined band structure of α-quartz with a Fermi level of -10.55 eV. The HOMO region consists in each case of nonbonding 2p-oxygen bands which in a localized language can be denoted as oxygen lone pairs ( | O<). We observe in each case the typical behaviour of an insulator with saturated valencies whose electronic structure can be described as being localized and is already present in the starting O_h-H₈Si₈O₁₂ molecule. The double-8-rings D8R of the _∞ ² [(-O)₄(Si₈O₁₂)] layer have a pore diameter of 4.1 Å, the same as the pore opening of zeolite A. It is large enough to accept up to four Ag, forming _∞ ² [(-O)₄(Si₈O₁₂)Ag_n], n = 1, 2, 3, 4, layers, suitable for modelling the electronic interactions between the zeolite cavity embedded silver clusters and between the clusters and the zeolite framework. With one Ag per D8R the band structure is simply a superposition of the 4d, 5s and 5p levels of a layer of nearly noninteracting Ag and the silicon dioxide layer. The Ag-d band lies below the oxygen lone pairs, the Ag-s band lies about 3 eV above the oxygen lone pairs, and the Ag-5p bands are in the antibonding silicon dioxide region. The first electronic transition is of oxygen lone pair to Ag-5s LMCT type. Increasing silver content results in progressive splitting of the 5σ Ag bands and shifts the first (Ag^m+ _n)? ← (| O<) charge transfer transition to lower energies. The filled Ag 4d-bands lie always significantly below the (| O<) HOCOs (highest occupied crystal orbitals) but their band width increases with increasing silver content. In all cases the zeolite environment separates the Ag clusters through antibonding Ag-(← O<) interactions so that the coupling remains weak and it makes sense to describe the Ag clusters in the D8R as quantum dots weakly interacting with each other.     

Experimental and DFT Evidence for the Fractional Non‐Innocence of a β‐Diketonate Ligand

New compounds [Ru(pap)₂(L)](ClO₄), [Ru(pap)(L)₂], and [Ru(acac)₂(L)] (pap=2‐phenylazopyridine, L^?=9‐oxidophenalenone, acac^?=2,4‐pentanedionate) have been prepared and studied regarding their electron‐transfer behavior, both experimentally and by using DFT calculations. [Ru(pap)₂(L)](ClO₄) and [Ru(acac)₂(L)] were characterized by crystal‐structure analysis. Spectroelectrochemistry (EPR, UV/Vis/NIR), in conjunction with cyclic voltammetry, showed a wide range of about 2 V for the potential of the Ru^III/II couple, which was in agreement with the very different characteristics of the strongly π‐accepting pap ligand and the σ‐donating acac^? ligand. At the rather high potential of +1.35 V versus SCE, the oxidation of L^? into L^. could be deduced from the near‐IR absorption of [Ru^III(pap)(L^.)(L^?)]²⁺. Other intense long‐wavelength transitions, including LMCT (L^?→Ru^III) and LL/CT (pap^.?→L^?) processes, were confirmed by TD‐DFT results. DFT calculations and EPR data for the paramagnetic intermediates allowed us to assess the spin densities, which revealed two cases with considerable contributions from L‐radical‐involving forms, that is, [Ru^III(pap⁰)₂(L^?)]²⁺?[Ru^II(pap⁰)₂(L^.)]²⁺ and [Ru^III(pap⁰)(L^?)₂]⁺?[Ru^II(pap⁰)(L^?)(L^?)]⁺. Calculations of electrogenerated complex [Ru^II(pap^.?)(pap⁰)(L^?)] displayed considerable negative spin density (?0.188) at the bridging metal.     

trans‐Bis(cyano‐κC)(1,4,8,11‐tetraazacyclotetradecane‐κ4N)manganese(III) perchlorate,a low‐spin manganese(III) complex

The crystal structure of the low‐spin (S = 1) Mn^III complex [Mn(CN)₂(C₁₀H₂₄N₄)]ClO₄, or trans‐[Mn(CN)₂(cyclam)](ClO₄) (cyclam is the tetradentate amine ligand 1,4,8,11‐tetra­aza­cyclo­tetra­decane), is reported. The structural parameters in the Mn(cyclam) moiety are found to be insensitive to both the spin and the oxidation state of the Mn ion. The difference between high‐ and low‐spin Mn^III complexes is that a pronounced tetragonal elongation of the coordination octahedron occurs in high‐spin complexes and a slight tetragonal compression is seen in low‐spin complexes, as in the title complex.     

Quecksilber(II)‐chlorid‐ und ‐iodid‐Komplexe von Dithia‐ und Tetrathiakronenethern

Mercury(II) Chloride and Iodide Complexes of Dithia‐ and Tetrathiacrown Ethers The complexes [(HgCl₂)₂((ch)₂30S₄O₆)] ( 1 ), [HgCl₂(mn21S₂O₅)] ( 2 ), [HgCl₂(ch18S₂O₄)] ( 3 ) and [HgI(meb12S₂O₂)]₂[Hg₂I₆] ( 4 ) have been synthesized, characterized and their crystal structures were determined. In [(HgCl₂)₂((ch)₂30S₄O₆)] two HgCl₂ units are discretely bonded within the ligand cavity of the 30‐membered dichinoxaline‐tetrathia‐30‐crown‐10 ((ch)₂30S₄O₆) forming a binuclear complex. HgCl₂ forms 1 : 1 “in‐cavity” complexes with the 21‐membered maleonitrile‐dithia‐21‐crown‐7 (mn21S₂O₅) ligand and the 18‐membered chinoxaline‐dithia‐18‐crown‐6 (ch18S₂O₄) ligand, respectively. The 12‐membered 4‐methyl‐benzo‐dithia‐12‐crown‐4 (meb12S₂O₂) ligand gave with two equivalents HgI₂ the compound [HgI(meb12S₂O₂)]₂[Hg₂I₆]. In the cation [HgI(meb12S₂O₂)]⁺ meb12S₂O₂ forms with the cation HgI⁺ a half‐sandwich complex.     

NiII and ZnII complexes of the hexadentate macrocyclic ligand cis‐6,13‐di­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐di­amine

The title pendent‐arm macrocyclic hexa­amine ligand binds stereospecifically in a hexadentate manner, and we report here its isomorphous Ni^II and Zn^II complexes (both as perchlorate salts), namely (cis‐6,13‐di­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐di­amine‐κ⁶N)­nickel(II) di­per­chlorate, [Ni(C₁₂H₃₀N₆)]­­(ClO₄)₂, and (cis‐6,13‐di­methyl‐1,4,8,11‐tetraaza‐cyclo­tetra­decane‐6,13‐di­amine‐κ⁶N)­zinc(II) di­per­chlorate, [Zn(C₁₂H₃₀N₆)]­(ClO₄)₂. Distortion of the N—M—N valence angles from their ideal octahedral values becomes more pronounced with increasing metal‐ion size and the present results are compared with other structures of this ligand.     

Synthese und Kristallstruktur des gemischt‐valenten Komplexes [Sn2I3(NPPh3)3]

Synthesis and Crystal Structure of the Mixed Valent Complex [Sn₂I₃(NPPh₃)₃] The mixed valent phosphoraneiminato complex [Sn₂I₃(NPPh₃)₃] ( 1 ) was prepared by the reaction of the tin(II) complex [SnI(NPPh₃)]₂ with sodium in tetrahydrofuran. 1 crystallizes with two formula units of THF to form yellow, moisture sensitive single crystals, which were characterized by a crystal structure determination. 1 · 2 THF: Space group P2₁/c, Z = 4, lattice dimensions at –80 °C: a = 1964.5(2), b = 1766.0(2), c = 2058.6(2) pm; β = 118.33(1)°, R = 0.052. 1 forms dimeric molecules in which the tin atoms are linked by two nitrogen atoms of two (NPPh₃^–) groups to form a planar Sn₂N₂ four‐membered ring. The Sn^IV atom is additionally coordinated by a terminal iodine atom and by a terminal (NPPh₃^–) group, whereas the Sn^II atom is additionally coordinated by two iodine atoms forming a ψ trigonal‐bipyramidal surrounding.