Neue Silber‐Tellurid Cluster stabilisiert mit zweizähnigen Phosphanen: Synthese und Struktur von {[Ag5(TePh)6(Ph2P(CH2)2PPh3)](Ph2P(CH2)2PPh2)}∞, [Ag18Te(TePh)15(Ph2P(CH2)3PPh2)3Cl] und [Ag38Te13(TetBu)12(Ph2P(CH2)2PPh2)3]

Novel Silver‐Telluride Clusters Stabilised with Bidentate Phosphine Ligands: Synthesis and Structure of {[Ag₅(TePh)₆(Ph₂P(CH₂)₂PPh₃)](Ph₂P(CH₂)₂PPh₂)}_∞, [Ag₁₈Te(TePh)₁₅(Ph₂P(CH₂)₃PPh₂)₃Cl], and [Ag₃₈Te₁₃(Te t Bu)₁₂(Ph₂P(CH₂)₂PPh₂)₃] Bidentate phosphine ligands have been found effective to stabilise polynuclear cores containing silver and chalcogenide ligands. They can act as intra and intermolecular bridges between the silver centres. The clusters {[Ag₅(TePh)₆(Ph₂P(CH₂)₂PPh₃)](Ph₂P(CH₂)₂PPh₂)}_∞ ( 1 ), [Ag₁₈Te(TePh)₁₅(Ph₂P(CH₂)₃PPh₂)₃Cl] ( 2 ), and [Ag₃₈Te₁₃(TetBu)₁₂(Ph₂P(CH₂)₂PPh₂)₃] ( 3 ) have been prepared and their molecular structure determined. Compound 2 and 3 are molecular structures with separated cluster cores while 1 forms a polymeric chain bridged by phosphine ligands. ( 1 : space group P2₁/c (No. 14), Z = 4, a = 3518,1(7) pm, b = 2260,6(5) pm, c = 3522,1(7) pm, β = 119,19(3)°; 2 : space group R3 (No. 148), Z = 6, a = b = 3059,4(4) pm, c = 5278,8(9) pm; 3: space group Pccn (No. 56), Z = 4, a = 3613,0(9) pm, b = 3608,6(7) pm, c = 2153,5(8) pm)     

Synthesis and Structural Characterization of [Cu20Se4(μ3‐SePh)12(PPh3)6] and [Ag(SePh)]∞

Reaction of lithium phenylselenothiolate, generated in situ from the reductive cleavage of PhSe‐SiMe₃ with alkyl lithium reagents and insertion of elemental sulfur, with triphenylphosphine solubilized CuCl affords the molecular cluster complex [Cu₂₀Se₄ (μ₃‐SePh)₁₂(PPh₃)₆] ( 1 ). The analogous reaction with AgCl yields the extended structure [Ag(SePh)]_∞ ( 2 ) in which an infinite layer of Ag^I atoms is capped on either side by μ₄‐SePh ligands. 1: space group P¯1, a = 17.9510(6), b = 18.1712(7), c = 31.4311(11) Å, a = 78.098(2), β = 82.905(2), γ = 70.012(2)°. 2: space group C2/c, a = 5.8762(6), b = 7.2989(7), c = 29.124(2) Å, β = 95.790(3)°.     

Neue Gold‐Selen‐Komplexverbindungen: Synthesen und Strukturen von [Au10Se4(dpppe)4]Br2, [Au2Se(dppbe)]∞, [(Au3Se)2(dppbp)3]Cl2 und [Au34Se14(tpep)6(tpepSe)2]Cl6

Novel Gold Selenium Complexes: Syntheses and Structures of [Au₁₀Se₄(dpppe)₄]Br₂, [Au₂Se(dppbe)]_∞, [(Au₃Se)₂(dppbp)₃]Cl₂, and [Au₃₄Se₁₄(tpep)₆(tpep^Se)₂]Cl₆ The reaction of gold phosphine complexes [(AuX)(PR₃)] (X= halogen; R = org. group) with Se(SiMe₃)₂ yield to new chalcogeno bridged gold complexes. Especially within the use of polydentate phosphine ligands cluster complexes like [Au₁₀Se₄(dpppe)₄]Br₂ ( 1 ) (dpppe = 1, 5‐Bis(diphenylphosphino)pentane), [Au₂Se(dppbe)]_∞ ( 2 ) (1, 4‐Bis(diphenylphosphino)benzene), [(Au₃Se)₂(dppbp)₃]Cl₂ ( 3 ) (dppbp = 4, 4′‐Bis‐diphenylphosphino)biphenyl) und [Au₃₄Se₁₄(tpep)₆(tpep^Se)₂]Cl₆ ( 4 ) (tpep = 1, 1, 1‐Tris(diphenylphosphinoethyl)phosphine, tpep^Se = 1, 1‐Bis(diphenylphosphinoethyl)‐1‐(diphenylselenophosphinoethylphosphine) could be isolated and their structures could be determined by X‐ray diffraction. ( 1: Space group P1 (No. 2), Z = 2, a = 1642.1(11), b = 1713.0(9), c = 2554.0(16) pm, α = 80.41(3)°, β = 76.80(4)°, γ = 80.92(4)°; 2: Space group P2₁/n (No. 14), Z = 4, a = 947.3(2), b = 1494.9(3), c = 2179.6(7) pm, β = 99.99(3)°; 3: Space group P2₁/c (No. 14), Z = 8, a = 2939.9(6), b = 3068.4(6), c = 3114.5(6) pm, β = 109.64(3)°; 4: Space group P1 (No. 2), Z = 1, a = 2013.7(4), b = 2420.6(5), c = 2462.5(5) pm, α = 77.20(3), β = 74.92(3), γ = 87.80(3)°).     

[Hg8(μ‐n‐C3H7Te)12(μ‐Br)Br3] — Synthesis and Structure

The novel mercury‐tellurium cluster [Hg₈(μ‐n‐C₃H₇Te)₁₂(μ₂‐Br)Br₃] is formed during the reaction of HgBr₂ and (n‐C₃H₇Te)₂Hg in DMSO. Its crystal structure has been elucidated showing [Hg₈(μ‐n‐C₃H₇Te)₁₂(μ₂‐Br)]³⁺ units with a bromine‐centered distorted Hg₈ cube. The mercury atoms are bridged by n‐C₃H₇Te^— ligands and the resulting clusters are linked to a three‐dimensional network by bromine atoms. The close packing of the cluster is mainly determined by the flexible n‐propyl residues of the telluride building blocks.     

Octahedral and Cyclic [Ag6] Cluster Cores Stabilized by {Ag3(Spz)3(N‐triphos)3} Motifs [HSpz = Pyrazine‐2‐thiolate,N‐triphos = Tris((diphenylphosphanyl)methyl)amine]: Ag···Ag Interactions

The complexes [Ag₁₂(Spz)₁₂(N‐triphos)₂][Ag₃(Spz)₃(N‐triphos)]₂ · (DMF)₆ ( 1 ) and [Ag₁₈(Spz)₁₂(N‐triphos)₄(CF₃CO₂)₆] ( 2 ) were synthesized and structurally characterized by X‐ray diffraction [HSpz = pyrazine‐2‐thiolate, N‐triphos = tris((diphenylphosphanyl)methyl)amine]. The central [Ag₆] ring with chair‐conformation in 1 and the ideally octahedral [Ag₆] cluster core in 2 are both stabilized by the tripodal building units of neutral [Ag₃(Spz)₃(N‐triphos)] compound. The Ag ··· Ag distances of the [Ag₆] moieties in 1 and 2 are 3.07 and 2.81 Å, respectively, exhibiting intermetallic interactions, which can enhance the stability of [Ag₆] conformations. In addition, the π ··· π interactions between parallel pyrazine rings could impose on the building and the Ag ··· Ag interactions of these Ag–S clusters.     

Münzmetallcluster mit verbrückenden Imido‐ und Amidoliganden: [{Li(dme)3}4][Cu18(NPh)11] und [Ag6(NHPh)4(PnPr3)6Cl2]

Copper and Silver Clusters with Bridging Imido and Amido Ligands From the reactions of copper and silver chloride with tertiary phosphines and lithiated aniline the compounds [{Li(dme)₃}₄][Cu₁₈(NPh)₁₁] ( 1 ) and [Ag₆(NHPh)₄(PⁿPr₃)₆Cl₂] ( 2 ) were obtained. The structure of the anion in 1 is closely related to the structures of the reported clusters [Cu₁₂(NPh)₈]^4– [1] and [Cu₂₄(NPh)₁₄]^4– [2]: 1 represents the third phenyl imido bridged copper cluster which contains parallel Cu₃‐ and Cu₆‐planes. The dimeric compound 2 consists of two Ag₃ units with bridging phenyl amido ligands. Two chloride and six phosphine ligands complete the ligand sphere and shield the metal core effectively.     

Synthese und Kristallstruktur des ersten Cp*‐geschützten Cobalttelluridclusters: Darstellung von [(Cp*Co)4(μ3‐Te)4] durch milde Oxidation von [Cp*CoCl]2 mittels Li4Sn2Te6 · 8 en

Synthesis and Crystal Structure of the First Known Cp* Ligated Cobalt Telluride Cluster: Mild Oxidation of [Cp*CoCl]₂ by Li₄Sn₂Te₆ · 8 en to give [(Cp*Co)₄(μ₃‐Te)₄] Oxidation of cobalt(II) complex [Cp*CoCl]₂ (Cp* = pentamethylcyclopentadiene) with binary Zintl polyanion hexatellurodistannate(IV) [Sn₂Te₆]^4– in Li₄Sn₂Te₆ · 8 en (en = 1,2‐diaminoethane) leads to the formation of the first Cp* ligated cobalt telluride cluster [(Cp*Co)₄(μ₃‐Te)₄]. The compound crystallizes as black cuboids that are suitable for X‐ray structural analysis. Space group P 1, lattice dimensions at 203 K: a = 1127.9(2), b = 1156.2(3), c = 1882.3(4) pm, α = 83.27(2), β = 83.24(2), γ = 66.11(1)°, V = 2222.3(9) · 10⁶ pm³, R₁ = 0.0681. The molecular structure of the compound features a Co₄Te₄ heterocubane and thus distributes to the completion of the series of known transition metal chalcogenide heterocubanes.     

Synthesen und Strukturen neuer amido- und imidoverbrückter Cobaltcluster: [Li(THF)2]3[Co3(μ2-NHMes)3Cl6] (1), [Li(DME)3]2[Co18(μ4-NPh)3(μ3-NPh)12Cl3] (2), [Li(DME)3]2[Co6(μ4-NPh)(μ2-NPh)6(PPh2Et)2] (3) und [Li(THF)4][Co8(μ3-NPh)6(μ2-NPh)3(PPh3)2] (4)

Syntheses and Crystal Structures of new Amido- und Imidobridged Cobalt Clusters: [Li(THF)₂]₃[Co₃(μ₂-NHMes)₃Cl₆] (1), [Li(DME)₃]₂[Co₁₈(μ₄-NPh)₃(μ₃-NPh)₁₂Cl₃] (2), [Li(DME)₃]₂[Co₆(μ₄-NPh)(μ₂-NPh)₆(PPh₂Et)₂] (3), and [Li(THF)₄][Co₈(μ₃-NPh)₆(μ₂-NPh)₃(PPh₃)₂] (4) The reactions of cobalt(II)-chloride with the lithium-amides LiNHMes and Li₂NPh leads to an amido-bridged multinuclear complex [Li(THF)₂]₃[Co₃(μ₂-NHMes)₃Cl₆] ( 1 ) as well as to the imido-bridged cobalt cluster [Li(DME)₃]₂[Co₁₈(μ₄-NPh)₃(μ₃-NPh)₁₂Cl₃] ( 2 ). In the presence of tertiary phosphines two imido-bridged cobalt clusters [Li(DME)₃]₂[Co₆(μ₄-NPh)(μ₂-NPh)₆(PPh₂Et)₂] ( 3 ) and [Li(THF)₄][Co₈(μ₃-NPh)₆(μ₂-NPh)₃(PPh₃)₂] ( 4 ) result. The structures of 1 – 4 were characterized by X-ray single crystal structure analysis.     

Selektive Darstellung zweifach diorganophosphido-verbrückter Metallatetrahedrane [Re2(MPR3)2(μ-PR2)2(CO)6] mit Re2M2-Metallgerüst (M = Au,Ag)

Selective Preparation of Twofold Diorganophosphido-bridged Metallatetrahedranes [Re₂(MPR₃)₂(μ-PR₂)₂(CO)₆] with Re₂M₂ Metal Core (M = Au, Ag) The reaction of the in situ prepared salt Li[Re₂(AuPR)(μ-PR₂)(CO)₇Cl] (R = R′ = Cy ( 1 a ), R = Cy, R′ = Ph ( 1 b ), R = Ph, R′ = Cy ( 1 c ), R = Ph, R′ = Et ( 1 d ), R = Ph, R′ = Ph ( 1 e )) with one equivalent HPR in methanolic solution at room temperature yields the neutral cluster complexes [Re₂(AuPR)(μ-PR₂)(CO)₇(ax-HPR) (R = R′ = R″ = Cy ( 2 a ), Ph ( 2 b ), R = R′ = Cy, R″ = Et ( 2 c ), R = Cy, R′ = R″ = Ph ( 2 d ), R = Cy, R′ = Ph, R″ = Et ( 2 e ), R = R″ = Ph, R′ = Et ( 2 f ), R = Ph, R′ = Cy, R″ = Et (2 g)). Photochemically induced these complexes react in the presence of the organic base DBU in THF solution to give the doubly phosphido bridged anions Li[Re₂(AuPR)(μ-PR₂)(μ-PR)(CO)₆], which were characterized as salts PPh₄[Re₂(AuPR)(μ-PR₂)(μ-PR)(CO)₆] (R = R′ = R″ = Ph ( 3 a ), R = R′ = Ph, R″ = Cy ( 3 b ), R = Ph, R′ = Cy, R″ = Et ( 3 c ), R = R″ = Ph, R′ = Et ( 3 d )). These precursor complexes 3 then react with one equivalent of ClMPR (M = Au, Ag) to doubly phosphido bridged metallatetrahedranes [Re₂(MPR₃)₂(μ-PR₂)(μ-PR)(CO)₆] (M = Au, R = R′ = R″ = Ph ( 4 a ), M = Au, R′ = Et, R = R″ = Ph ( 4 b ), M = Au, R = R′ = Ph, R″ = Cy ( 4 c ), M = Au, R = Cy, R′ = Ph, R″ = Et ( 4 d ), M = Ag, R = R′ = R″ = Ph ( 4 e )). All isolated cluster complexes were characterized and identified by the following analytical methods: NMR- (¹H, ³¹P) and ν(CO) IR-spectroscopy and, additionally, complexes 2 b , 4 a and 4 e by X-ray structure analysis.     

Synthese und Strukturen neuer selenido‐ und selenolatoverbrückter Kupfercluster: [Cu38Se13(SePh)12(dppb)6] (1), [Cu(dppp)2][Cu25Se4(SePh)18(dppp)2] (2), [Cu36Se5(SePh)26(dppa)4] (3), [Cu58Se16(SePh)24(dppa)6] (4) und [Cu3(SeMes)3(dppm)] (5)

Syntheses and Crystal Structures of new Selenido‐ and Selenolato‐bridged Copper Clusters: [Cu₃₈Se₁₃(SePh)₁₂(dppb)₆] (1), [Cu(dppp)₂][Cu₂₅Se₄(SePh)₁₈(dppp)₂] (2), [Cu₃₆Se₅(SePh)₂₆(dppa)₄] (3), [Cu₅₈Se₁₆(SePh)₂₄(dppa)₆] (4), and [Cu₃(SeMes)₃(dppm)] (5) The reactions of copper(I) chloride or copper(I) acetate with monodentate phosphine ligands (PR₃; R = organic group) and Se(SiMe₃)₂ have already lead to the formation of CuSe clusters with up to 146 copper and 73 selenium atoms. If the starting materials and the bidentate phosphine ligands (Ph₂P–(CH₂)_n–PPh₂, n = 1: dppm, n = 3: dppp, n = 4: dppb; Ph₂P–C≡C–PPh₂: dppa) and silylated chalcogen derivates are changed (RSeSiMe₃; R = Ph, Mes) a series of new CuSe clusters can be synthesized. From single crystal X‐ray structure analysis one can characterise [Cu₃₈Se₁₃(SePh)₁₂(dppb)₆] ( 1 ), [Cu(dppp)₂] · [Cu₂₅Se₄(SePh)₁₈(dppp)₂] ( 2 ), [Cu₃₆Se₅(SePh)₂₆(dppa)₄] ( 3 ), [Cu₅₈Se₁₆(SePh)₂₄(dppa)₆] ( 4 ) and [Cu₃(SeMes)₃(dppm)] ( 5 ). In this new class of CuSe clusters, compounds 1 and 4 possess a spherical cluster skeleton, wheras 2 and 3 have a layered cluster core.     

Thallium(I), Silver(I), and Mixed Thallium(I)/Copper(I) Clusters with Bridging {Me2Si(N‐C6H4‐2‐SPh)2}2– Ligands

The S‐functionalized aminosilane Me₂Si(NH‐C₆H₄‐2‐SPh)₂ (H₂L) ( 1 ) was prepared from dichlorodimethylsilane and lithiated 2‐(phenylthio)aniline. Treatment of compound 1 with two equivalents of n‐butyllithium led to the dilithium derivative Li₂L, which was used in subsequent reactions with MCl (M = Tl, Cu, Ag) to prepare the complexes [Tl₂L] ( 2 ), [Cu₂Tl₂L₂] · 2THF ( 3a ), [Cu₂Tl₂L₂(THF)₂] ( 3b ), and [Ag₄L₂(THT)₂] ( 4 ) (THT = tetrahydrothiophene). Compound 2 consists of two thallium atoms, which are connected by a L^2– ligand to give a puckered Tl₂N₂ ring with Tl–N distances of 255(1)–268(1) pm. Compounds 3a and 3b are heterobimetallic complexes, which are based on [Cu₂L₂]^2– cores featuring a Cu₂N₄Si₂ ring with linearly coordinated copper atoms [Cu–N: 190.7(3)–192.5(3) pm] and two peripherally attached Tl atoms [Tl–N: 272.7(3)–281.9(3) pm]. The molecular structure of the tetranuclear silver(I) complex 4 is closely related to the structure of compounds 3a and 3b by replacement of the Cu and Tl atoms with Ag atoms. The Ag–N distances are 217.5(3)–245.7(3) pm.     

Synthese,Kristallstruktur und spektroskopische Charakterisierung von [Au12(PPh)2(P2Ph2)2(dppm)4Cl2]Cl2

Synthesis, Crystal Structure and Spectroscopic Characterization of [Au₁₂(PPh)₂(P₂Ph₂)₂(dppm)₄Cl₂]Cl₂ The reaction of [(AuCl)₂dppm] (dppm = Ph₂PCH₂PPh₂) with P(Ph)(SiMe₃)₂ in CHCl₃ results in the formation of [Au₁₂(PPh)₂(P₂Ph₂)₂(dppm)₄Cl₂]Cl₂ ( 1 ), the crystal structure of which was determined by single crystal X‐ray analysis (space group P2₁/c, a = 1425.3(3) pm, b = 2803.7(6) pm, c = 2255.0(5) pm, β = 95.00(3)°, V = 8977(3)·10⁶ pm³, Z = 2). The dication in 1 consists of two Au₆P₃ units built by highly distorted Au₃P and Au₂P₂ heterotetrahedra, connected via four bidentate phosphine ligands. Additionally, the compound was characterized by IR‐, UV‐ and NMR spectroscopy. The ³¹P{¹H} NMR spectrum is discussed in detail.     

Synthese und Strukturen von [Cu8As3(AsSiMe3)2(dppb)4]+‐[Cu{As2(SiMe3)2}{As4(SiMe3)4}]‐, [Cu8As3(AsSiMe3)2(dppb)4]+‐[Cu{As(SiMe3)2}2]‐ und [Cu10(Sb3)2(SbSiMe3)2(dppm)6]

The reaction of CuCl, LiAs(SiMe₃)₂ and dppb (Bis(diphenylphosphino)butane) leads to the formation of ionic cluster complexes. Depending on the reaction conditions one can isolate [Cu₈As₃(AsSiMe₃)₂(dppb)₄]⁺[Cu{As₂(SiMe₃)₂}{As₄(SiMe₃)₄}]^‐ ( 1 ) and [Cu₈As₃(AsSiMe₃)₂(dppb)₄]⁺[Cu{As(SiMe₃)₂}₂]^‐ ( 2 ). The same reaction of CuCl, dppm (Bis(diphenylphosphino)methane) and LiSb(SiMe₃)₂ leads to the neutral cluster complex [Cu₁₀(Sb₃)₂(SbSiMe₃)₂(dppm)₆] ( 3 ). The structures of 1‐3 have been solved by X‐ray single crystal analyses.     

Cobalt Chalcogenide Clusters. Synthesis,Characterization and DFT Calculations of [Co4Se2(CO)10] and [Co4Te2(CO)11]. Crystal Structure of [Co8Se4(CO)16(μ‐dppa)2]

The reactions of [Co₂(CO)₈] with E(SiMe₃)₂ (E = Se, Te) in CH₂Cl₂ result in the formation of the compounds [Co₄Se₂(CO)₁₀]> ( 1 ) and [Co₄Te₂(CO)₁₁] ( 2 ), respectively. Both cluster complexes have similar molecular structures in which the cobalt atoms form four‐membered rings with μ₄‐bridging chalcogen atoms (Se and Te) above and below the plane of the metal atoms and the carbonyl ligands as either terminal or μ₂‐bridging ligands. DFT‐calculations for both compounds have been carried out in order to obtain some more information about their electronic distribution. In the presence of the phosphine Ph₂PC≡CPPh₂ (dppa), the reaction of [Co₂(CO)₈] with Se(SiMe₃)₂ leads to the formation of [Co₈Se₄(CO)₁₆(μ‐dppa)₂] ( 3 ). During the reaction two molecules of [Co₂(CO)₈] have been added to the acetylene groups of the dppa ligands, whilst the remaining cobalt atoms coordinate to the phosphorus atoms of the phosphine. In this compounds the selenium atoms act as μ₃‐ligands, bridging the metal atoms bonded to the phosphorus with those bonded to the acetylene groups.     

Kupferkomplexe des neuen Chelatliganden 1‐Methyl‐2‐(2‐thiophenolato)‐1H‐benzimidazol (mtpb) und dessen Oxidationsprodukten

Copper Complexes of the New Chelate Ligand 1‐Methyl‐2‐(2‐thiophenolato)‐1H‐benzimidazole (mtpb) and of its Oxidation Products Anodic electrolysis of copper in acetonitrile in the presence of Hmtpb leads to formation of yellow [Cu₄(mtbp)₄] which was crystallized as a dichloromethane solvate with two crystallographically independent cluster molecules in the unit cell. The copper(I) atoms exhibit slightly pyramidal S₂N coordination with bridging thiolate sulfur atoms. The two clusters contain the four copper atoms arranged in a more (Cu1‐Cu4) or less (Cu5‐Cu8) distorted bisphenoidal arrangement. Reaction of mtpb^— with Cu(ClO₄)₂ under anoxic conditions also produces [Cu₄(mtpb)₄]. However, the admittance of O₂ in the reaction of mtpb^— with copper(II) acetate in methanol causes oxidation of the sulfur atoms; a square‐pyramidal configurated copper(II) complex [Cu(CH₃CO₂‐κ²O)(L₁‐κN)(L₂‐κN, O)] has been isolated and crystallographically characterized in which L₁ is the neutral sulfinic methyl ester and L₂^— is the sulfonate derived from mtpb^—.     

Synthesen und Kristallstrukturen von Cu‐ und Ag‐Komplexen mit [Ta6S17]4—‐Ionen als Liganden

Syntheses and Crystal Structures of Cu and Ag Complexes with [Ta₆S₁₇]^4— Ions as Ligands In the presence of phosphines saturated solutions of the thiotantalates (NEt₄)₄[(Ta₆S₁₇)] · 3MeCN react with copper or silver salts to give new heterobimetallic Ta—M—S clusters (M = Ag, Cu). These clusters contain the intact cluster core of the [Ta₆S₁₇]^4— anion. Compounds [Cu(PMe₃)₄]₃[(Ta₆S₁₇)Cu(PMe₃)] · 2MeCN ( 1 ), (NEt₄)[(Ta₆S₁₇)Ag₃(PMe₂ⁱPr)₆] · 5MeCN ( 2 ), [(Ta₆S₁₇)Cu₄ (PMe₂ⁱPr)₈] · MeCN ( 3 ), [(Ta₆S₁₇)Cu₅Cl(PMe₂ⁱPr)₉] · MeCN ( 4 ) and [Ta₂Cu₂S₄Cl₂(PMe₂ⁱPr)₆] · 2MeCN ( 5 ) are presented herein. The structures of these compounds were elucidated by single crystal X‐ray structural analyses.     

[(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 .