Die Kristallstrukturen von (DDI)2[Sb2F6O] und (DDI)2[Sb3F7O2] (DDI = 1, 3‐Diisopropyl‐4, 5‐dimethylimidazolium) — Ein Beitrag zur Hydrolyse von SbF3 [1]

The Crystal Structures of (DDI)₂[Sb₂F₆O] and (DDI)₂[Sb₃F₇O₂] (DDI = 1,3‐Diisopropyl‐4,5‐dimethylimidazolium) — a Contribution to the Hydrolysis of SbF₃ [1] The salts (DDI)₂[Sb₂F₆O] ( 2 ) and (DDI)₂[Sb₃F₇O₂] ( 3 ), (DDI = 1,3‐diisopropyl‐4,5‐dimethylimidazolium) are obtained by hydrolysis of C₁₁H₂₀N₂SbF₃ ( 1 ). The anion [Sb₂F₆O]^2? consists of two SbF₂ fragments linked by a symmetrical oxygen bridge and two unsymmetrical fluorine bridges to form a distored ψ‐octahedral coordination sphere at the antimony atoms. In [Sb₃F₇O₂]^2?, two SbF₂ units are linked by a symmetrical fluorine bridge, while the third antimony atom is connected with each SbF₂ fragment by a symmetrical oxygen and an unsymmetrical fluorine bridge. The antimony atoms adopt the centres of strongly distored ψ‐polyhedra.     

[{C8H12Rh}3(μ3‐OH)2]SbF6: Ein neuer metallorganischer Rhodiumkomplex mit Rh3O2‐Kern

[{C₈H₁₂Rh}₃(μ₃‐OH)₂]SbF₆: A New Organometallic Rhodium Complex with Rh₃O₂ Core Crystals of C₂₄H₃₈F₇O₂Rh₃Sb ( 3 ) obtained from the crystallisation of 2 from wet solvents consist of [{C₈H₁₂Rh}₃(μ₃‐OH)₂]⁺ cations connected with the SbF₆^– anions via hydrogen bonds. In the cations, the Rh₃ faces are bicapped by OH^– ligands.     

Polymorphism of Ph2P(CH2Py)(NSiMe3) and the Staudinger Reaction of Ph2P(CH2Py) with Hydrogenazide1)

A new polymorph of the iminophosphorane Ph₂P(CH₂Py)(NSiMe₃), ( 1 ), is compared to a just recently published. The reaction of the starting material, the phosphane Ph₂P(CH₂Py) with N₃SiMe₃ in the presence of water gives [Ph₂P(CH₂Py)(NH₂)][N₃], ( 2 ). A comparison of the structural and NMR parameters of 2 with previously reported derivatives of 1 , suggests that 2 is best described as a phosphonium salt in which the negatively charged imino nitrogen atom is protonated, according to [Ph₂(CH₂Py)P⁺—NH₂][N₃]^—, rather than as an iminiumphosphane salt [Ph₂(CH₂Py)P=⁺NH₂][N₃]^—.     

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)     

Complexes of Cu2(μ‐OAc)4(H2O)2 with 1,10‐Phenanthroline and Comparison with those of 2,2′‐Bipyridine. Crystal Structure of the Dimer [Cu(OAc)2(phen)](μ‐H2O)

The two complexes of composition Cu₂(OAc)₄(phen)(H₂O)₂ ( 1 ) andCu₂(OAc)₄(phen)₂(H₂O) ( 2 ) have been synthesized and characterized by chemical analysis and IR and electronic spectroscopies. Compound 2 has the structure of a dimer with a phenanthroline molecule and two monodentate acetate groups coordinated to each copper atom and a water molecule as the only bridging ligand between them. Each copper atom has a distorted square‐planar pyramidal coordination, determined by two oxygen atoms at 1.94(3) and 1.959(3) Å, two nitrogen atoms at 2.023(4) Å and the oxygen atom of the bridging water molecule at 2.289(2) Å. The distance between the two copper atoms is of 4.29 Å and the angle Cu(1)‐O(3)‐Cu(1A) 139.2(2)°. The water molecule is involved in two intramolecular hydrogen bonds with non coordinated oxygen atoms. The distance between the molecules of phenanthroline is 3.75 Å. Magnetic and EPR results for Cu₂(OAc)₄(phen)(H₂O)₂ ( 1 ), Cu₂(OAc)₄(phen)₂(H₂O) ( 2 ), Cu₂(OAc)₄(bipy) ( 3 ) and Cu₂(OAc)₄(bipy)₂(H₂O)₂ ( 4 ) have been analysed and compared. For 1 and 3 an antiferromagnetic dimer unit [Cu₂(μ‐OAc)₄] with 2J = ?325 and ?292 cm^?1, respectively, and other two copper atoms without significant magnetic interaction are present. Triplet signals are detected in the EPR spectra. In 2 and 4 there is no practically magnetic exchange and the orthorhombic signals are observed in the EPR spectra.     

On the Reaction of [(CO)3Fe(μ‐Me2NCO)2Fe(CO)2(NHMe2)] with Chelating Ligands — X‐Ray Structures of New Binuclear μ‐Carbamoyl Complexes

Reaction of the binuclear μ‐carbamoyl complex [(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)₂(HNMe₂)] ( 1 ) in toluene with the chelating ligands Ph₂PCH₂PPh₂ (dppm) and Ph₂PCH₂CH₂PPh₂ (dppe) gives different results. With dppm only the complex [(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)₂(dppm)] ( 3 ) with a dangling ligand is obtained under replacement of amine, whereas with dppe depending on the reaction conditions up to three compounds are found. A 1 : 1 mixture of the educts generates the related complex [(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)₂(dppe)] ( 4 ) together with the tetranuclear complex [{(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)₂}₂(dppe)] (5 ). 4 slowly converts into [(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)(dppe)] ( 6 ) with dppe acting as a chelating ligand. 6 is the first compound in this series in which one of the five CO groups is replaced by another donor. A 2 : 1 molar ratio of 1 and dppe quantitatively produces 5 . Addition of CO to a solution of 6 proceeds under slow reversible conversion of the complex into 4 . The compounds were characterized by the usual spectroscopic methods; 3 , 5 and 6 were also studied by X‐ray diffraction analyses.     

Synthese,NMR‐Spektren und Molekülstruktur von [(CH3)2Ga{μ‐P(H)Si(CH3)3}2Ga(CH3)2{μ‐P(Si(CH3)3)2}Ga(CH3)2]

Synthesis, NMR Spectra and Structure of [(CH₃)₂Ga{μ‐P(H)Si(CH₃)₃}₂Ga(CH₃)₂{μ‐P(Si(CH₃)₃)₂}Ga(CH₃)₂] The title compound has been prepared in good yield by the reaction of [Me₂GaOMe]₃ (Me = CH₃) with HP(SiMe₃)₂ in toluene (ratio 1 : 1,1) and purified by crystallization from pentane or toluene, respectively. This organogallium compound forms (Ga–P)₃ ring skeletons with one Ga–P(SiMe₃)₂–Ga and two Ga–P(H)SiMe₃–Ga bridges and crystallizes in the monoclinic space group C2/c. The known homologous Al‐compound is isotypic, both (M^III–P)₃ heterocycles have twist‐conformations, the ligands of the monophosphane bridges have trans arrangements.     

Synthesis and Characterization of Pyrrolthiosemicarbazone Complexes of Palladium(II). Crystal Structures of [{Pd[C4H4NC(H)=NNC(S)NHMe](Cl)}2{μ‐Ph2P(CH2)3PPh2}] and [Pd{C4H4NC(H)=NNC(S)NHMe}{Ph2P(CH2)2PPh2‐P,P}](Cl)

Reaction of the thiosemicarbazone ligands C₄H₄NC(H)=NN(H)C(S)NHR (R = Me, a ; Et, b ) with Li₂[PdCl₄] gave the dinuclear complexes [Pd{C₄H₄NC(H)=NNC(S)NHR}(μ‐Cl)]₂ (R = Me, 1a ; Et, 1b ) with a central Pd₂Cl₂ core and with deprotonation of the thiosemicarbazones at the hydrazinic nitrogen atom. Treatment of 1a and 1b with triphenylphosphine gave the mononuclear compounds [Pd{C₄H₄C(H)=NNC(S)NHR}(Cl)(PPh₃)] (R = Me, 2a ; Et, 2b ), whereas reaction of 1a and 1b with tertiary diphosphines gave mono‐ and dinuclear compounds, as appropriate, with the corresponding diphosphine acting as a monodentate ( 6b ), chelating ( 3a ) and bridging ligand ( 4a, 5a , 4b, 5b ). Treatment of 1a and 1b with (Ph₂PCH₂CH₂PPh₂)W(CO)₅ gave the new heterobimetallic complexes 7a and 7b . The crystal structures of complexes 3a and 4a are described.     

[Fc2B2(Br)(μ‐NPEt3)2]+Br– – ein Ferrocenyl‐substituierter Phosphaniminato‐Komplex des Bors

[Fc₂B₂(Br)(μ‐NPEt₃)₂]⁺Br^– – a Ferrocenyl‐substituted Phosphoraneiminato Complex of Boron [Fc₂B₂(Br)(μ‐NPEt₃)₂]⁺Br^– has been prepared from ferrocenylboron dibromide, [Fe(η⁵‐C₅H₅)(η⁵‐C₅H₄BBr₂)], and the silylated phosphoraneimine Me₃SiNPEt₃ in dichloromethane solution to give orange‐red single crystals which were characterized by IR, NMR and ⁵⁷Fe Mössbauer spectra, as well as by a crystal structure determination. [Fc₂B₂(Br)(μ‐NPEt₃)₂]⁺Br^– · 3 CH₂Cl₂ ( 1 · 3 CH₂Cl₂): Space group P2₁/n, Z = 4, lattice dimensions at –50 °C: a = 1370.6(3), b = 2320.9(5), c = 1454.4(2), β = 95.38(1)°, R₁ = 0.061. In the cation of 1 the ferrocenyl‐substituted boron atoms are connected by the nitrogen atoms of the [NPEt₃]^– groups to form a planar B₂N₂ four‐membered ring. One of the boron atoms having planar, the other tetrahedral coordination.     

Über die Kristallstrukturen der Cyanokomplexe [Co(NH3)6][Fe(CN)6], [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O und [Cu(en)2][Ni(CN)4]

On the Crystal Structures of the Cyano Complexes [Co(NH₃)₆][Fe(CN)₆], [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O, and [Cu(en)₂][Ni(CN)₄] Of the three title compounds X‐ray structure determinations were performed with single crystals. [Co(NH₃)₆][Fe(CN)₆] (a = 1098.6(6), c = 1084.6(6) pm, R3, Z = 3) crystallizes with the CsCl‐like [Co(NH₃)₆][Co(CN)₆] type structure. [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O (a = 805.7(5), b = 855.7(5), c = 1205.3(7) pm, α = 86.32(3), β = 100.13(3), γ = 90.54(3)°, P1, Z = 1) exhibits a related cation lattice, the one cavity of which is occupied by one anion and 2 H₂O, whereas the other contains two anions parallel to each other with distance Ni…Ni: 423,3 pm. For [Cu(en)₂][Ni(CN)₄] (a = 650.5(3), b = 729.0(3), c = 796.5(4) pm, α = 106.67(2), β = 91.46(3), γ = 106.96(2)°, P1, Z = 1) the results of a structure determination published earlier have been confirmed. The compound is weakly paramagnetic and obeys the Curie‐Weiss law in the range T < 100 K. The distances within the complex ions of the compounds investigated (Co–N: 195.7 and 196.4 pm, Ni–C: 186.4 and 186.9 pm, resp.) and their hydrogen bridge relations are discussed.     

[2+4] and [2+2] Cycloaddition Reactions of N‐Sulfinyl Carboxylic Acid Amides with (CF3)2BNMe2. Crystal Structure of cyclo‐(CF3)2B‐NMe2‐S(=O)‐N=C(p‐CH3C6H4)‐O

N‐sulfinylacylamides R‐C(=O)‐N=S=O react with (CF₃)₂BNMe₂ ( 1 ) to form, by [2+4] cycloaddition, six‐membered rings cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(R)‐O for R = Me ( 2 ), t‐Bu ( 3 ), C₆H₅ ( 4 ), and p‐CH₃C₆H₄ ( 5 ) while N‐sulfinylcarbamic acid esters R‐O‐C(=O)‐N=S=O react with 1 to yield mixtures of six‐membered (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(OR)‐O) and four‐membered rings (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N(C=O)OR) for R = Me ( 6 and 9 ), Et ( 7 and 10 ), and C₆H₅ ( 8 and 11 ). The structure of 5 has been determined by X‐ray diffraction.     

Die Kristallstruktur von (Ph4P)2[Be4Cl4(μ‐N3)6]

Suitable single crystals for X‐ray analysis of the recently published azido beryllate (Ph₄P)₂[Be₄Cl₄(μ‐N₃)₆] ( 1 ) [1] were obtained by a modified synthetic route, and the crystal structure of 1 was determined. The compound crystallizes isotypically with the corresponding bromo derivative [1] in the space group C2/c with 12 formula units per unit cell. Lattice dimensions at 193 K: a = 4125.5(1), b = 2001.7(1), c = 2050.4(1) pm, β = 101.05 (1)°, R₁ = 0.0359. The structure contains adamantanlike dianions [Be₄Cl₄(μ‐N₃)₆]^2? with a Be₄N₆ core forming by the bridging function of the α‐nitrogen atoms of the azido groups.     

Fluoroborates by Cleavage of Trimethylamine‐bis(trifluoromethyl)boranes with NEt3 × 3 HF. Structures of C6F5(CF3)2B · NMe3, K[C6H5CH2(CF3)2BF], and K[C6H5(CF3)2BF]

Trimethylamine‐bis(trifluoromethyl)boranes R(CF₃)₂B · NMe₃ (R = cis/trans‐CF₃CF=CF ( 1/2 ), HC≡C ( 3 ), H₂C=CH ( 4 ), C₂H₅ ( 5 ), C₆H₅CH₂ ( 6 ), C₆F₅ ( 7 ), C₆H₅ ( 8 )) react with NEt₃ × 3 HF depending on the nature of R at 155–200 °C under replacement of the trimethylamine ligand to form the corresponding fluoro‐bis(trifluoromethyl)borates [R(CF₃)₂BF]^– ( 1 a/2 a – 8 a ). The structures of 7 , K[C₆H₅CH₂(CF₃)₂BF] ( K‐6 a ), and K[C₆H₅(CF₃)₂BF] ( K‐8 a ) have been investigated by single‐crystal X‐ray diffraction. In 7 the CF₃ groups make short repulsive contacts with NMe₃ and C₆F₅ entities – the B–CF₃ bonds being unusually long. The B–F bond lengths of K‐6 a and K‐8 a (1.446(3) and 1.452(2) Å, respectively) are long for a fluoroborate.     

Azidokomplexe von Vanadium(IV) und Vanadium(V): (Ph4P)2[VOCl2(μ‐N3)]2 und (Ph4P)2[VOCl(μ‐N3)(N3)2]2

Azido Complexes of Vanadium(IV) and Vanadium(V): (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ and (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ ( 1 ) was prepared by reaction of (Ph₄P)[VO₂Cl₂] with trimethylsilylazide in the molar ratio 1:2 in dichloromethane solution to give dark green, moisture sensitive, non‐explosive single crystals. The reaction is accompanied by the formation of the dark blue side‐product (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ ( 2a ), which can be obtained as the main product by application of a large excess of Me₃SiN₃. Dark blue needles of 2a crystallize spontaneously from the CH₂Cl₂ solution within one hour at 4 °C. After standing at 4 °C under its mother liquid within 24 hours a first‐order phase transition of 2a occurs forming dark blue prismatic single crystals of 2b . According to single crystal X‐ray structure determinations, 2a and 2b crystallize in the same type of space group , however, with different lattice dimensions. The vanadium(IV) complex 1 is characterized by X‐ray structure determination and by vibrational spectroscopy (IR, Raman) as well as by EPR spectroscopy, whereas 2b is characterized by IR spectroscopy. 1 : Space group P2₁/n, Z = 2, a = 1009.5(1), b = 1226.6(2), c = 1943.0(2) pm, β = 98.42(1)°, R₁ = 0.0672. The complex anion forms centrosymmetric units with V₂N₂‐four‐membered rings with a V···V distance of 335.6(1) pm and coordination number five on the vanadium(IV) atoms. 2a : Space group , Z = 1, a = 1089.0(2), b = 1097.1(2), c = 1310.1(2) pm, α = 92.99(1)°, β = 106.12(2)°, γ = 117.05(2)°, V = 1309.8(4) ų, d_calc. = 1.440 g·cm^?3, R₁ = 0.0384. The complex anion forms centrosymmetric units of symmetry C_i with V₂N₂ four‐membered rings and VN bond lengths of 200.4(3) and 234.4(2) pm, respectively. The non‐bonding V···V distance amounts to 356.2(1) pm. 2b : Space group , Z = 1, a = 1037.3(2), b = 1157.6(2), c = 1177.2(2) pm, α = 98.48(2)°, ° = 103.82(2)°, γ = 106.33(2)°, V = 1281.8(4) ų, d_calc. = 1.471 g·cm^?3, R₁ = 0.0724. The structure of the complex anion is similar to the anion of 2a with VN bond lengths of the four‐membered V₂N₂ ring of 203.3(4) and 235.2(4) pm, respectively, and a non‐bonding V···V distance of 357.5(1) pm.     

Synthesis and Structure of the Clusters [Hg2(μ—SePh)2(SePh)2(PPh3)2] and [Hg3Br3(μ—SePh)3] · 2 DMSO

The compounds [Hg₂(μ—SePh)₂(SePh)₂(PPh₃)₂] ( I ) and [Hg₃Br₃(μ—SePh)₃] · 2 DMSO ( II ) are formed by reactions of [Hg(SePh)₂] with PPh₃ in THF( I ) or with HgBr₂ in DMSO ( II ) at room temperature. X—ray crystallography reveals that the cluster I consists of a distorted square built by each two Hg and Se atoms. The Hg atoms have almost tetrahedral co‐ordination environments formed by selenium atoms of two (μ‐^—SePh) ligands and Se and P atoms of terminal ^—SePh and PPh₃ ligands. The compound II is a six‐membered ring with alternating Hg and Se atoms in the chair conformation. Two DMSO molecules occupy positions below and above the [Hg₃Se₃] ring with the oxygen atoms directed to the centre of the ring.     

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.     

Molekül‐ und Kristallstruktur von Bis[chloro(μ‐phenylimido)(η5‐pentamethylcyclopentadienyl)tantal(IV)](Ta–Ta), [{TaCl(μ‐NPh)Cp*}2]

Molecular and Crystal Structure of Bis[chloro(μ‐phenylimido)(η⁵‐pentamethylcyclopentadienyl)tantalum(IV)](Ta–Ta), [{TaCl(μ‐NPh)Cp*}₂] Despite the steric hindrance of the central atom in [TaCl₂(NPh)Cp*] (Ph = C₆H₅, Cp* = η⁵‐C₅(CH₃)₅), caused by the Cp* ligand, the imido‐ligand takes a change in bond structure when this educt is reduced to the binuclear complex [{TaCl(μ‐NPh)Cp*}₂] in which tantalum is stabilized in the unusual oxidation state +4.     

Palladium(II) Complexes with the Mixed‐Donor Ligand CH3S‐(CH2)3‐PPh2 Crystal Structures of [PdCl2{CH3S‐(CH2)3‐PPh2}n](n = 1, 2)

The phosphorus‐sulfur ligand 1‐(methylthio)‐3‐(diphenylphosphino)‐propane (S‐P3) has been synthesized and characterized by ¹H NMR and ¹³C NMR. Reactions of S‐P3 with [PdCl₂(PhCN)₂] afforded the complexes [PdCl₂(S‐P3)] ( I ) and [PdCl₂(S‐P3)₂] ( II ), in which S‐P3 acts as a bidentate and monodentate ligand, respectively. Compound I crystallizes in monoclinic space group P2₁/n (No. 14) with cell dimensions: a = 8.589(3), b = 15.051(3), c = 17.100(3)Å, β = 102.91(2)°, V = 2154.7(9)ų, Z = 4. Likewise, compound II crystallizes in monoclinic space group P2₁/n (No. 14) with a = 9.993(5), b = 8.613(4), c = 18.721(5)Å, β = 90.18(3)°, V = 1611.3(12)ų, Z = 2. Compound II has a trans square planar configuration with only the P‐site of the ligand bonded to the palladium atom.     

Neue Azidokomplexe des Tantals(V). Synthese und Molekülstruktur der Zweikernverbindungen [Cp*TaCl(N3)(μ‐N3)]2(μ‐O) und [Cp*Ta(N3)3(μ‐N3)]2 (Cp* = Pentamethylcyclopentadienyl)

New Azido Complexes of Tantalum(V). Synthesis and Molecular Structure of the Dinuclear Compounds [Cp*TaCl(N₃)(μ‐N₃)]₂(μ‐O) and [Cp*Ta(N₃)₃(μ‐N₃)]₂ (Cp* = Pentamethylcyclopentadienyl) The reaction of Cp*TaCl₄ ( 1 ) with an excess of trimethylsilyl azide (Me₃Si–N₃) leads to azide‐rich dinuclear complexes which contain both terminal and bridging azido ligands. The oxo complex [Cp*TaCl(N₃)(μ‐N₃)]₂(μ‐O) ( 4 ) was formed in dichloromethane in the presence of traces of water, whereas [Cp*Ta(N₃)₃(μ‐N₃)]₂ ( 5 ) was obtained from boiling toluene after several days. According to the X‐ray structure determinations the Ta…Ta distance in 4 (314,5 pm) is considerably shorter than in 5 (382,2 pm).     

“Cage‐like” Carboxyl Bridged Octaphenyltetraantimony Compounds (SbPh2)4(μ‐O)4(μ‐OH)2(μ‐O2CR)2: Synthesis and Structural Characterization

The metal‐directed self‐assembly of biphenylantimony trichloride and homocarboxylic acids LH [L = 2‐CHO‐C₆H₄COO^– ( 1 ), 2, 3‐2F‐C₆H₄COO^– ( 2 ), 4‐CF₃–C₆H₄COO^– ( 3 )] provided three novel tetranuclear organoantimony(V) complexes, which were characterized by elemental analysis, FT‐IR, ¹H, and ¹³C NMR spectroscopy as well as melting point, and X‐ray single crystal analysis. In the molecular structure, four hexacoordinate antimony atoms are linked into a [Sb₂(μ‐O)₂]₂(μ‐O)₂ “cage” architecture by oxo‐bridges which are terminally bridged by two carboxyl groups.