[(TeMe2)Mn(CO)4(μ5-Te)(μ4-Te)Mn4(CO)12]−: A Pentacoordinate Bridging Tellurido Ligand in a Square-Pyramidal Geometry

The first Te–Mn–CO clusters were obtained by the thermal reaction of K₂TeO₃ with [Mn₂(CO)₁₀] in MeOH. The basicity of the μ₄-Te ligand in the octahedral cluster anion [(μ₄-Te)₂Mn₄(CO)₁₂]²⁻ is demonstrated by its binding to the fragment [(TeMe₂)Mn(CO)₄]⁺ in an axial fashion to afford the novel cluster 1 .     

Synthesis and Structural Characterization of Manganese Carbonyl Incorporated Polyoxomolybdate (n-Bu_4N)_2[Mo_6O_(16)(OCH_3)_2{HOCH_2C(CH_2O)_3}_2{Mn(CO)_3}_2]

The polyoxoanion incorporated {Mn(CO)3+} complex, (n-Bu4N)2[Mo6O16(OCH3)2{HOCH2C(CH2O)3}2· {Mn(CO)3}2](1), has been synthesized by the reaction of (n-Bu4N)4[Mo8O26] with Mn(CO)5Br in methanol, in the presence of C(CH2OH)4. The complex 1 has been characterized by IR, UV-Vis, X-ray single crystal diffraction, and TG. Crystal data for the complex 1: C25H48MnMo3NO16 (1), Triclinic P1, a=0.9405(3) nm, b=1.3351(4) nm, c=1.5455(4) nm, α=103.206(5)o, β=102.165(5)o, γ=100.784(5)o, V=1.7896(9) nm3, Z=2, R1=0.0703, wR...     

Synthesis and Characterization of Manganese(I) Carbonyl Complexes of the Type [(OC)4Mn{μ‐P(R)Aryl}]2

Metalation of secondary phosphanes HPRR′ [R = R′ = C₆H₄‐4‐Me, C₆H₃‐3,5‐Me₂ ( 3 ), C₆H₄‐4‐NMe₂ ( 4 ); R/R′ = Ph/cHex] with Mn₂(CO)₁₀ in boiling xylene (mixture of isomers), until the evolution of gaseous carbon monoxide ceases, leads to the formation of the dinuclear complexes of the type [(OC)₄Mn(μ‐PRR′)]₂ [R = R′ = C₆H₄‐4‐Me ( 5 ), C₆H₃‐3,5‐Me₂ ( 6 ), R/R′ = Ph/cHex ( 7 ), R = R′ = C₆H₄‐4‐NMe₂ ( 8 )] with poor to moderate yields. These manganese(I) complexes are only sparingly soluble or even nearly insoluble in hydrocarbons at room temperature. Planar four‐membered Mn₂P₂ rings represent the central moiety with four carbonyl ligands at each manganese(I) atom. The steric demand of the P‐bound substituents influences the Mn–P bond lengths as well as the P–Mn–P bond angles.     

[Te8]2[Ta4O4Cl16]: A Two‐dimensional Tellurium Polycation obtained via Ionic Liquid‐Based Synthesis

By reaction of elemental tellurium, tellurium(IV) chloride, tantalum(V) chloride and tantalum(V) oxychloride in the ionic liquid [BMIM]Cl ([BMIM]Cl:1‐Butyl‐3‐methylimidazolium chloride),[Te₈]₂[Ta₄O₄Cl₁₆] is obtained in the form of lucent black crystals. The title compound consists of infinite [Te–Te–(Te₆)]_n²⁺ chains (Te–Te: 264.9(1)–284.3(1) pm) and isolated [Ta₄O₄Cl₁₆]^4– anions. The [Te–Te–(Te₆)]_n²⁺ chains are interconnected to form a two‐dimensional tellurium network (Te–Te: 335.9 pm). Due to this interaction the [Te–Te–(Te₆)]_n²⁺ chains in [Te₈]₂[Ta₄O₄Cl₁₆] show an arrangement that differs significantly from known polycationic [Te₈]_n²⁺ chains. The two‐dimensional tellurium network is finally separated by tetrameric, corner‐sharing oxidochloridotantalate anions [(TaO_2/2Cl_4/1)₄]^4– that are firstly observed. The composition of [Te₈]₂[Ta₄O₄Cl₁₆] is confirmed by EDX analysis; its optical band gap is estimated to 1.1–1.2 eV via UV/Vis spectroscopy.     

Synthesis and Crystal Structure of Manganese‐tris(1,2‐ethanediamine)tetratelluride [Mn(en)3]Te4 Exhibiting Intermolecular Interactions between the Tetratelluride Anions

Air‐sensitive black crystals of the new compound [Mn(en)₃]Te₄ were synthesized by reacting MnCl₂ · 4 H₂O, K₂Te₃ and elemental Te in 1,2‐ethanediamine (en) under solvothermal conditions at 433 K. The compound crystallizes in the monoclinic space group P2₁/n with lattice parameters a = 839.51(7) pm, b = 1551.3(1) pm, c = 1432.6(1) pm, and β = 90.28(2)°. Isolated [Mn(en)₃]²⁺ cations and Te₄^2– anions are arranged in an alternating fashion parallel to the crystallographic b‐axis. One terminal Te atom of the Te₄^2– anions exhibits a short intermolecular contact to a neighboured anion thus forming Te₈^4– anions. A slightly longer interionic Te…Te separation is observed between two of the inner Te atoms of neighboured Te₈^4– anions. Taking these longer separations into account infinite Te‐chains are formed running parallel to [001]. The intermolecular Te…Te interactions affect the Te–Te bond lengths within the Te₄^2– anion leading to a lengthening of the average Te–Te distance. Short N–H…Te distances indicate hydrogen bonding between the cations and anions. DTA‐TG measurements show that at 441 K the material decomposes in one step. The resulting crystalline material consists of MnTe₂ and Te.     

The Ylide Adduct SOC2(PPh3)2 as Complex Ligand. Reaction with [Mn2(CO)10] and InCl3; Crystal Structures of [(CO)4Mn(SOC2{PPh3}2)2][Mn(CO)5] and (H2C{PPh3}2)[InCl4]2

The betain‐like SOC₂(PPh₃)₂ ( 1a ) reacts with [Mn₂(CO)₁₀] in THF to produce the salt‐like complex [(CO)₄Mn(SOC₂{PPh₃}₂)₂][Mn(CO)₅] ( 2 ). 1a is bonded via the sulfur atoms which are arranged in trans position in the octahedral environment of the manganese atom. With InCl₃ from CH₂Cl₂ solution the addition product [Cl₃In(SOC₂{PPh₃}₂)] ( 3 ) is obtained along with the salt (H₂C{PPh₃}₂)[InCl₄]₂ ( 4 ), which is the result of proton abstraction from the solvent. The crystal structures of 2· 0.5THF and 4· CH₂Cl₂ are reported. The compounds are further characterized by IR and ³¹P NMR spectroscopy.     

Polytellurides and Polyselenides – Compounds Containing $_{\infty}^{1}\rm [Te_{6}-Te_{4}]^{4-}$ and [Sn(Se4)3]2− Anions

The reactions of the Zintl phase K₂Cs₂Sn₉ with elemental tellurium and selenium in ethylenediamine have been investigated. From the reaction of K₂Cs₂Sn₉ with elemental tellurium [K‐(2,2,2‐crypt)]₄Te₆Te₄ ( 2 ) and [K‐(2,2,2‐crypt)]₂Sn₂Te₃ ( 3 ) were obtained, whereas the reaction of K₂Cs₂Sn₉ with elemental selenium led to the formation of [K‐(2,2,2‐crypt)]₂Sn(Se₄)₃ ( 4 ) and [K‐(2,2,2‐crypt)]₂Cs₂Sn₂Se₆·2en ( 5 )¹⁾. Compounds 2 , 4 , 5 have been characterized by single crystal X‐ray structure determination.     

The First Orthotelluric Acid Polysilylesters: Synthesis and Crystal Structure of [(Me3SiO)8Te2O2] and [(Me4Si2O2)3Te]

The compounds [(Me₃SiO)₈Te₂O₂] ( 1 ) and [(Me₄Si₂O₂)₃Te] ( 2 ) have been prepared in good yields through Bronsted acid‐base reaction of Te(OH)₆ with Me₃SiNEt₂ and Me₄Si₂(NEt₂)₂, respectively. They have been characterised by multinuclear NMR spectroscopy and single crystal X‐ray diffraction analyses. The formation of dinuclear 1 is the result of fast intermolecular condensation of two partially silylated orthotelluric acid units during the esterification process. Its structure consists of two edge‐fused TeO₆‐octahedra, bearing a four‐membered Te₂O₂ ring as central motif. In contrast, the main structural feature of chiral 2 is a TeO₆ octahedron which is fully silylated by three bidentate 1,1,2,2‐tetramethyldisilanediyl units, resulting in a racemic mixture. The metastability of 2 is remarkable since the Te(+ 6) center usually acts as a strong oxidation reagent toward the Si–Si bond in disilanes. 1 and 2 represent potential starting compounds for molecular Te_xO_y aggregates as hybrid components for new glasses by sol‐gel procedure.     

Formation of the Salt‐like Complexes [Co{S2CC(PPh3)2}3][Co(CO)4]3 and [(CO)4Mn{S2CC(PPh3)2}][Mn(CO)5] from the Reaction of the Related Carbonyl Compounds with S2CC(PPh3)2

The betain‐like compound S₂CC(PPh₃)₂ ( 1 ), which is obtained from CS₂ and the double ylide C(PPh₃)₂, reacts with [Co₂(CO)₈] and [Mn₂(CO)₁₀] in THF to afford the salt‐like complexes [Co{S₂CC(PPh₃)₂}₃][Co(CO)₄]₃ ( 2 ) and [(CO)₄Mn{S₂CC(PPh₃)₂}][Mn(CO)₅] ( 3 ), respectively, in good yields. At both d⁶ cations 1 acts as a chelating ligand. Disproportionation reactions from formal Co⁰ into Co^III and Co^?I and from Mn⁰ into Mn^I and Mn^?I occurred with the removal of four or one carbonyl groups, respectively. The crystal structures of 2· 5.5THF and 3· 2THF are reported, which show a shortening of the C–C bond in the ligand upon complex formation. The compounds are further characterized by ³¹P NMR and IR spectroscopy.     

Die Kristallstruktur des Diacetonalkohol‐Komplexes [Mn(DAA)3]2+[MnI4]2– · DAA

Crystal Structure of the Diacetone Alcohol Complex [Mn(DAA)₃]²⁺[MnI₄]^2– · DAA The title compound has been prepared from MnI₂ and excess diacetone alcohol (4‐hydroxy‐4‐methyl‐2‐pentanon) to give brown single crystals which were suitable for a crystal structure determination. Space group P2₁/c, Z = 4, lattice dimensions at 157 K: a = 1158.3(1), b = 1806.0(1), c = 1846.5(2) pm, β = 97.421(8)°, R₁ = 0.0381. The structure consists of [Mn(DAA)₃]²⁺ ions with distorted octahedral environment of the manganese atom, tetrahedral [MnI₄]^2– ions and a diacetone alcohol molecule which is connected by two hydrogen bridges with the complex cation.     

The Reaction of the Betain‐like Compound O2C2(PPh3)2 with [(cod)PtI2] – Crystal Structure of the Salt (HC{PPh3}2)[(η3‐C8H11)PtI2]

The reaction of the betain‐like compound O₂C₂(PPh₃)₂ ( 1 ) with [(cod)PtX₂] in THF solution gives the salt‐like compounds (HC{PPh₃}₂)[(η³‐C₈H₁₁)PtX₂] ( 3 , X = I; 4 , X = Cl) in about quantitative yields. The new η³‐bonded C₈H₁₁ ligand is the result of a proton transfer from the coordinated cod ligand to 1 with subsequent release of CO₂. The X‐ray analysis of 3 shows the presence of two isomers in a 60:40 ratio, which differ in the bonding of the C₈H₁₁ ligand. 3 crystallizes in the triclinic space group with the unit cell dimensions a = 1091.7(1), b = 1141.5(1), c = 1649.4(2) pm; α = 80.34(1)°, β = 83.62(1)°, γ = 89.03(1)°, V = 2013.7(4)·10⁶ pm³, Z = 2.     

On the Complexes of Bis(trifluoromethyl)ditellurium,Te2(CF3)2, with Halide Ions – A Crystallographic Study of the Pseudo‐trihalides [PNP][(TeCF3)2X] (PNP = Bis(triphenylphosphoranyliden)ammonium; X = Cl,Br, I)

The anions [(TeCF₃)₂X]^? (X = Cl, Br, I) resemble the trihalides [I₂X]^? in the solid state and show similar dynamic behaviour in solution. All three compounds crystallize iso‐structurally in the triclinic space group with Z = 2 and exhibit cell dimensions according to the sizes of the halogen atoms.     

Concerning the Reaction of the Betain‐Like Compound O2CC(PPh3)2 with Tungsten‐Carbonyl Derivatives; Preparation and Crystal Structures of [(CO)5W{η1‐O2C2(PPh3)2}] and [(CO)4W{η2‐O2C2(PPh3)2}]

The carbodiphosphorane CO₂ adduct O₂CC(PPh₃)₂ ( 1a ) reacts with [(CO)₅W(THF)] and [(CO)₃W(NCEt)₃] to produce the complexes [(CO)₅W{η¹‐O₂CC(PPh₃)₂}] ( 2 ) and [(CO)₄W{η²‐O₂CC(PPh₃)₂}] ( 3 ), respectively. Whereas in 2 the betain‐like ligand is coordinated at the tungsten atom in a monodentate manner, in 3 it acts as a chelating ligand with formation of a WO₂C four‐membered ring. As a by‐product during the reaction with the acetonitrile adduct also some crystals of the hydrolysis product [HC(PPh₃)₂]₂[W₆O₁₉] · 3C₂H₄Cl₂ (4 · 3C₂H₄Cl₂) were isolated. All compounds could be characterized by X‐ray analyses and the usual spectroscopic methods.     

Double Carbonyl Substitution in [BrMn(CO)5]: Reaction with Benzoylhydrazine and Synthesis of fac‐[Mn(Br)(CO)3(BHD)]·2THF (BHD = OC(Ph)—NH—NH2)

[BrMn(CO)₅] reacts with benzoylhydrazine in THF occurring substitution of two CO groups by a Metal‐ligand ring to give fac‐[Mn(Br)(CO)₃(BHD)]·2THF (BHD = C₆H₅CONHNH₂). The novel compound shows a distorted octahedral arrangement at the manganese atom, with three nearly linear carbonyl ligands in a fac arrangement, illustrating another example that the CO group in position trans to the bromine ligand in [BrMn(CO)₅] presents the most intensive metal‐CO backbonding effect of all the CO groups of the parent complex, leading to the formation of a facial (and not meridional) isomer, even in the presence of a bidentate ligand like benzydrazide. X‐ray measures of yellow crystals showed that the title complex belong to space group P2₁/c, with the asymmetric unit containing one crystallographically independent [Mn(Br)(CO)₃(BHD)] complex and two tetrahydrofurane solvate molecules. The new compound represents heretofore the unique occurrence of the complexing single bidentate ligand ‐O=C(Ph)‐N(H)‐N(H)₂‐ with an octahedral coordination at the Mn^I atom supported chiefly by carbonyl groups.     

The Structure of Tris(trifluoromethyl)tellurium Fluoride Dimethylformamide, $\rm [Te(CF_{3})_{3} \times DMF(\mu-F)]{\infty}$

represents the first structurally characterized example of a trifluoromethyl main group element compound with more than 8‐N (where N is the main group number) perfluoroalkyl groups and also the first fluoro(triorgano)tellurium derivative. Its polymeric nature is caused by asymmetric bridging fluorine atoms forming infinite chains.     

Copper(II) and Manganese(II) Coordination Polymers of 5‐Aminobenzene‐1,3‐dicarboxylic Acid (abdc) Ligand,Structural Studies of [Cu(μ4‐abdc) (DMF)]n and {[Mn(μ4‐abdc)(H2O)]·H2O}n

Two new two‐dimensional Cu^II and Mn^II coordination polymers of 5‐aminobenzene‐1,3‐dicarboxylic acid (abdc) ligand, [Cu(μ₄‐abdc)(DMF)]_n and {[Mn(μ₄‐abdc)(H₂O)]·H₂O}_n, have been synthesized and characterized by elemental analysis and IR‐ spectroscopy. The single crystal X‐ray analyses show that the coordination number in these complexes is six, CuO₅Cu and MnO₅N. The compounds are structurally diverse and the coordination polymer obtained from copper show significant copper–copper interaction while the manganese coordination polymer shows Mn–N_amino bond.     

Koordinativ ungesättigte Dirutheniumkomplexe: Synthese und Kristallstrukturen von [Ru2(CO)n(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (n = 4; 5) und [Ru2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)]

Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐ray Crystal Structures of [Ru₂(CO)_n(μ‐H)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] (n = 4; 5) and [Ru₂(CO)₄(μ‐CH₂)(μ‐H)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] The reaction of [Ru₂(μ‐CO)(CO)₅(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 2 ) with dppm yields the dinuclear species [Ru₂(μ‐CO)(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 3 ) (dppm = Ph₂PCH₂PPh₂). Under thermal or photolytic conditions 3 loses very easily one carbonyl ligand and affords the corresponding electronically and coordinatively unsaturated complex [Ru₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 4 ). 4 is also obtainable by an one‐pot synthesis from [Ru₃(CO)₁₂], an excess of ^tBu₂PH and stoichiometric amounts of dppm via the formation of [Ru₂(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)₂] ( 1 ). 4 exhibits a Ru–Ru double bond which could be confirmed by addition of methylene to the dimetallacyclopropane [Ru₂(CO)₄(μ‐CH₂)(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 5 ). The molecular structures of 3 , 4 and 5 were determined by X‐ray crystal structure analyses.     

Tellurium‐Halogen Secondary Bonding in the Crystal Structures of [Q]+[PhTeCl4]— (Q = C5NH6, 2‐Br‐C5NH5, {2‐Br‐C5NH5}{Co(NH3)4Cl2})

The reaction of diphenylditelluride with pyridine, 2‐bromopyridine or 2‐bromopyridine/tetraamminedichlorocobalt(III) chloride in 12 M hydrochloric acid afforded the tetrachlorophenyltellurate(IV) compounds [C₅NH₆][PhTeCl₄] ( 1 ), [2‐Br‐C₅NH₅] [PhTeCl₄] ( 2 ), and [{2‐Br‐C₅NH₅}{Co(NH₃)₄Cl₂}] [PhTeCl₄]₂ ( 3 ). They were all characterized structurally by single crystal X‐ray diffraction. In all structures, the arrangement about the tellurium atoms is square pyramidal. The [PhTeCl₄]^— anions in 1 and 2 form trimeric and dimeric units, respectively, through Te···Cl secondary bonding. Compound 3 shows an unusual face‐to‐face packing of the [PhTeCl₄]^—anions with hydrogen bonding to the bromopyridium cation.     

Synthese und Eigenschaften von Ph3Sn‐substituierten Telluraten – Die Kristallstrukturen von trans‐[(Ph3SnO)4Te(OH)2] und trans‐[(Ph3SnO)2Te(OMe)4]

The reaction of Te(OH)₆ with Ph₃SnOH in ethanol leads to the formation of trans‐[(Ph₃SnO)₄Te(OH)₂] ( 1 ). Compound 1 crystallizes triclinic in the space group P\bar{1} with a = 996.6(2) pm, b = 1365.4(3) pm, c = 1368.2(3) pm and α = 71.15(2)°, β = 71.48(2)°, γ = 74.81(3)° (at 220 K). The molecular structure of 1 consists of a tellurium atom, which is coordinated nearly octahedrally by four Ph₃SnO units and two hydroxyl groups that are trans to each other. The Te–O bond lengths are in the range of 190.5(2) and 193.7(2) pm. Treatment of 1 with methanol under reflux yields trans‐[(Ph₃SnO)₂Te(OMe)₄] ( 2 ). Compound 2 crystallizes triclinic in the space group P\bar{1} with a = 1012.8(1) pm, b = 1422.4(2) pm, c = 1618.1(2) pm, and α = 100.44(1)°, β = 107.92(1)°, γ = 110.66(1)° (at 220 K). 2 forms centrosymmetric molecules in which the tellurium atom is surrounded nearly octahedrally by four methoxy groups and two trans arranged Ph₃SnO units. The Te–O bond lengths of 187.9(3)–194.5(3) pm are similar to those observed in 1 .     

Diiodobis(diphenyltelluride)mercury(II), [(Ph2Te)2HgI2]

Diiodobis(diphenyltelluride)mercury(II), [(Ph₂Te)₂HgI₂], is formed during the reaction of [(PhTe)₂Hg] with HgI₂ in refluxing THF. The same product can be obtained from a pressure reaction between PhTeI₃ and elemental mercury. The mercury atom is co‐ordinated in a distorted tetrahedral environment with I‐Hg‐I angles of 117?. Long range I···Te contacts of about 3.8 Å link the [(Ph₂Te)₂HgI₂] units to infinite chains along the b axis of the unit cell.