A 3d‐4f Complex Constructed by the Assembly of a Cationic Template, [Cu(en)2]2+, and a 3D Anionic Coordination Polymer, [Sm2(C2O4)3(C5O5)(H2O)2]2–

A three‐dimensional (3D) 3d‐4f complex, [Cu(en)₂][Sm₂(C₅O₅)(C₂O₄)₃(H₂O)₂] · 8H₂O ( 1 ) (en = ethylenediamine, C₅O₅^2– = dianion of 4,5‐dihydroxycyclopent‐4‐ene‐1,2,3‐trione), were prepared via the in‐situ ring‐opening oxidation reaction of croconate in the presence of the template‐directed complex, [Cu(en)₂]²⁺ cation. The structural characterization determined by X‐ray diffraction determination reveals that the 3D anionic coordination polymer of [Sm₂(C₂O₄)₃(C₅O₅)(H₂O)₂]^2– in 1 can be describe in terms of in‐plane 2D honeycomb‐like [Sm₂(C₂O₄)₃] layered frameworks bridged by oxalate with bis‐chelating mode, being mutually interlinked via the bridge of μ_1,2,3,4‐croconate ligands with bis‐chelating coordination mode to complete the 3D open framework, which gives rise to 1D channels with pore size of 14.023 × 11.893 Å (longest atom–atom contact distances) along the b axis. The structure‐directing complex, [Cu(en)₂]²⁺, and solvated water molecules are resided into these honeycomb‐type hexagonal channels. The thermal stability of 1 was further studied by TGA and in‐situ powder X‐ray diffraction measurement.     

Water de/adsorption associated with single‐crystal‐to‐single‐crystal structural transformation of a series of two‐dimensional metal–organic frameworks, [M(bipy)(C4O4)(H2O)2]·3H2O (M = Mn (1), Fe (2), and Zn (3), and bipy=4,4′‐bipyridine)

An assembly of three metal coordination polymers (CPs), [M(bipy)(C₄O₄)(H₂O)₂]·3H₂O (M = Mn ( 1 ), Fe ( 2 ), Zn ( 3 ), and bipy = 4,4′‐bipyridine, C₄O₄^2? (squarate) = dianion of H₂C₄O₄ (squaric acid)), was synthesized and structurally characterized. Single‐crystal X‐ray structural determination reveals that compounds 1 – 3 are iso‐structural, in which the M(II) ions are six‐coordinate in a distorted octahedral geometry. C₄O₄^2? and bipy both act as bridging ligands with bis‐monodentate coordination mode connecting the M(II) ions to form a two‐dimensional (2D) layered metal–organic framework (MOF). Adjacent 2D layers are then arranged in parallel and interpenetrated manners to construct their three‐dimensional (3D) supramolecular architecture. Compounds 1 , 2 , and 3 undergo two‐step dehydration processes with the first and second weight losses of 14.1 and 8.6% for 1 , of 12.1 and 7.5% for 2, and of 11.2 and 8.1% for 3 , respectively, corresponding to the weight losses of the three guest water molecules and the two coordinated water molecules, and all exhibit reversible sponge‐like water de/adsorption properties during de/rehydration processes for guest water molecules as per cyclic thermogravimetric analysis (TGA). The single‐crystal‐to‐single‐crystal (SCSC) structural transformation during the reversible de/rehydration processes of three guest water molecules was identified and monitored using exhaustive single‐crystal and powder X‐ray diffraction measurements.     

Saure Sulfate des Neodyms: Synthese und Kristallstruktur von (H5O2)(H3O)2Nd(SO4)3 und (H3O)2Nd(HSO4)3SO4

Acidic Sulfates of Neodymium: Synthesis and Crystal Structure of (H₅O₂)(H₃O)₂Nd(SO₄)₃ and (H₃O)₂Nd(HSO₄)₃SO₄ Light violett single crystals of (H₅O₂)(H₃O)₂ · Nd(SO₄)₃ are obtained by cooling of a solution prepared by dissolving neodymium oxalate in sulfuric acid (80%). According to X‐ray single crystal investigations there are H₃O⁺ ions and H₅O₂⁺ ions present in the monoclinic structure (P2₁/n, Z = 4, a = 1159.9(4), b = 710.9(3), c = 1594.7(6) pm, β = 96.75(4)°, R_all = 0.0260). Nd³⁺ is nine‐coordinate by oxygen atoms. The same coordination number is found for Nd³⁺ in the crystal structure of (H₃O)₂Nd(HSO₄)₃SO₄ (triclinic, P1, Z = 2, a = 910.0(1), b = 940.3(1), c = 952.6(1) pm, α = 100.14(1)°, β = 112.35(1)°, γ = 105.01(1)°, R_all = 0.0283). The compound has been prepared by the reaction of Nd₂O₃ with chlorosulfonic acid in the presence of air. In the crystal structure both sulfate and hydrogensulfate groups occur. In both compounds pronounced hydrogen bonding is observed.     

Synthese und Kristallstruktur von K2(HSO4)(H2PO4), K4(HSO4)3(H2PO4) und Na(HSO4)(H3PO4)

Synthesis and Crystal Structure of K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄), and Na(HSO₄)(H₃PO₄) Mixed hydrogen sulfate phosphates K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄) and Na(HSO₄)(H₃PO₄) were synthesized and characterized by X‐ray single crystal analysis. In case of K₂(HSO₄)(H₂PO₄) neutron powder diffraction was used additionally. For this compound an unknown supercell was found. According to X‐ray crystal structure analysis, the compounds have the following crystal data: K₂(HSO₄)(H₂PO₄) (T = 298 K), monoclinic, space group P 2₁/c, a = 11.150(4) Å, b = 7.371(2) Å, c = 9.436(3) Å, β = 92.29(3)°, V = 774.9(4) ų, Z = 4, R₁ = 0.039; K₄(HSO₄)₃(H₂PO₄) (T = 298 K), triclinic, space group P 1, a = 7.217(8) Å, b = 7.521(9) Å, c = 7.574(8) Å, α = 71.52(1)°, β = 88.28(1)°, γ = 86.20(1)°, V = 389.1(8)ų, Z = 1, R₁ = 0.031; Na(HSO₄)(H₃PO₄) (T = 298 K), monoclinic, space group P 2₁, a = 5.449(1) Å, b = 6.832(1) Å, c = 8.718(2) Å, β = 95.88(3)°, V = 322.8(1) ų, Z = 2, R₁ = 0,032. The metal atoms are coordinated by 8 or 9 oxygen atoms. The structure of K₂(HSO₄)(H₂PO₄) is characterized by hydrogen bonded chains of mixed H_nS/PO₄^– tetrahedra. In the structure of K₄(HSO₄)₃(H₂PO₄), there are dimers of H_nS/PO₄^– tetrahedra, which are further connected to chains. Additional HSO₄^– tetrahedra are linked to these chains. In the structure of Na(HSO₄)(H₃PO₄) the HSO₄^– tetrahedra and H₃PO₄ molecules form layers by hydrogen bonds.     

Hybrid Inorganic‐Organic Frameworks: Synthesis and Crystal Structures of RbFe(SO4)(C2O4)0.5·H2O and CsM(SO4)(C2O4)0.5·H2O (M = Mn,Fe)

Three new alkali metal transition metal sulfate‐oxalates, RbFe(SO₄)(C₂O₄)_0.5 · H₂O and CsM(SO₄)(C₂O₄)_0.5 · H₂O (M = Mn, Fe) were prepared through hydrothermal reactions and characterized by single‐crystal X‐ray diffraction, solid state UV/Vis/NIR diffuse reflectance spectroscopy, infrared spectra, thermogravimetric analysis, and powder X‐ray diffraction. The title compounds all crystallize in the monoclinic space group P2₁/c (no. 14) with lattice parameters: a = 7.9193(5), b = 9.4907(6), c = 8.8090(6) Å, β = 95.180(2)°, Z = 4 for RbFe(SO₄)(C₂O₄)_0.5 · H₂O; a = 8.0654(11), b = 9.6103(13), c = 9.2189(13) Å, β = 94.564(4)°, Z = 4 for CsMn(SO₄)(C₂O₄)_0.5 · H₂O; and a = 7.9377(3), b = 9.5757(4), c = 9.1474(4) Å, β = 96.1040(10)°, Z = 4 for CsFe(SO₄)(C₂O₄)_0.5 · H₂O. All compounds exhibit three‐dimensional frameworks composed of [MO₆] octahedra, [SO₄]^2– tetrahedra, and [C₂O₄]^2– anions. The alkali cations are located in one‐dimensional tunnels.     

[Gd(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O的晶体结构和生物活性

在水乙醇混合溶剂中，首次得到了2-羰基丙酸水杨酰腙、1，10-菲啰啉与硝酸钆形成的配合物[Gd(C₁₀H₉N₂O₄)(C₁₀H₈N₂O₄)(H₂O)₃]₂·phen·4H₂O，并测试了其单晶结构。该配合物属三斜晶系，空间群为P-1。每个配合物分子中有两个九配位的钆的结构单元，每个钆离子与两个三齿配体2-羰基丙酸水杨酰腙（分别以负一价和负二价形式）和三个水分子配位。每个钆单元在空间呈扭曲的单帽四方反棱柱。同时还有一个游离的1，10-菲啰啉存在于晶格中，通过氢键与配位水作用。生物活性试验表明该配合物对三种病原菌有一定的抑菌活性。     

Macromolecular Self‐Assembly of Organotin(IV) Squarates and Croconates – Preparation and Crystal Structures of [SnMe2(H2O)2]C4O4, [SnMe3]2C4O4, and [SnMe3(H2O)]2C5O5

The new organotin(IV) squarates and croconates [SnMe₂(H₂O)₂]C₄O₄ ( 1 ), [SnMe₃]₂C₄O₄ ( 2 ), and [SnMe₃(H₂O)]₂C₅O₅ ( 3 ), were prepared by salt metathesis from the appropriate sodium salts, and characterized by single‐crystal X‐ray diffraction and infrared spectroscopy. While 1 and 2 are coordination polymers with bridging C₄O₄^2– anions, compound 3 exists as a monomer in the solid state. In the hydrated compounds 1 and 3 , the molecules are interconnected by various types of O–H ··· O bridges between non‐coordinated carbonyl oxygen atoms and water ligands, resulting in a supramolecular layer ( 1 , 2 ) or network structure ( 3 ), respectively.     

A Novel Mixed‐Ligand Manganese(II) Complex Containing a V‐shape Water Trimer: Synthesis,Structure and Magnetic Properties of {[Mn(azpy)2(dca)(H2O)2](ClO4)(azpy)(H2O)2}n

A novel mixed‐ligand complex {[Mn(azpy)₂(dca)(H₂O)₂](ClO₄)(azpy)(H₂O)₂}_n ( 1 ) has been synthesized and characterized by single crystal X‐ray analysis, elemental analysis, IR spectroscopy and variable temperature magnetic measurement. The 4,4′‐azopyridine and dicyanamide ligands are abbreviated as azpy and dca, respectively. The crystal structure of 1 revealed that the 1D covalent bonding chains constructed by μ_1,5‐dca bridging the Mn^II ions are linked together via O–H···N and O–H···O hydrogen bonds and π‐π stacking interactions into a 3D supramolecular structure. V‐shape (bent) water trimers were also found in the structure. The water clusters play an important role in the formation of the 3D supramolecular structure. The determination of the variable temperature magnetic susceptibilities (2–300 K) shows the existence of a very weak antiferromagnetic interaction with a J value of ?0.16 cm^?1.     

M3+(H2AsO4)(H2As2O7) (M3+ = Al,Ga) and In2(H2AsO4)2(H2As2O7)2: a new layer structure type and a new framework structure type containing the rare H2As2O72− group

The crystal structures of hydrothermally synthesized aluminium dihydrogen arsenate(V) dihydrogen diarsenate(V), Al(H₂AsO₄)(H₂As₂O₇), gallium dihydrogen arsenate(V) dihydrogen diarsenate(V), Ga(H₂AsO₄)(H₂As₂O₇), and diindium bis[dihydrogen arsenate(V)] bis[dihydrogen diarsenate(V)], In₂(H₂AsO₄)₂(H₂As₂O₇)₂, were determined from single‐crystal X‐ray diffraction data collected at room temperature. The first two compounds are representatives of a novel sheet structure type, whereas the third compound crystallizes in a novel framework structure. In all three structures, the basic building units are M ³⁺O₆ octahedra (M = Al, Ga, In) that are connected via one H₂AsO₄⁻ and two H₂As₂O₇²⁻ groups into chains, and further via H₂As₂O₇²⁻ groups into layers. In Al/Ga(H₂AsO₄)(H₂As₂O₇), these layers are interconnected by weak‐to‐medium–strong hydrogen bonds. In In₂(H₂AsO₄)₂(H₂As₂O₇)₂, the H₂As₂O₇²⁻ groups link the chains in three dimensions, thus creating a framework topology, which is reinforced by weak‐to‐medium–strong hydrogen bonds. The three title arsenates represent the first compounds containing both H₂AsO₄⁻ and H₂As₂O₇²⁻ groups.     

Synthesis,Reactivity and Crystal Structures of the Palladium(II) Complexes with the Pyrimidine Containing Ligand: Crystal Structures of [Pd(PPh3)(η1‐C4H3N2)(η2‐S2CNC4H8)] and [Pd(PPh3)(η1‐C4H3N2)(η2‐Tp)]

Treatment of Pd(PPh₃)₄ with 5‐bromo‐pyrimidine [C₄H₃N₂Br] in dichloromethane at ambient temperature cause the oxidative addition reaction to produce the palladium complex [Pd(PPh₃)₂(η¹‐C₄H₃N₂)(Br)], 1 , by substituting two triphenylphosphine ligands. In acetonitrile solution of 1 in refluxing temperature for 1 day, it do not undergo displacement of the triphenylphosphine ligand to form the dipalladium complex [Pd(PPh₃)Br]₂{μ,η²‐(η¹‐C₄H₃N₂)}₂, or bromide ligand to form chelating pyrimidine complex [Pd(PPh₃)₂(η²‐C₄H₃N₂)]Br. Complex 1 reacted with bidentate ligand, NH₄S₂CNC₄H₈, and tridentate ligand, KTp {Tp = tris(pyrazoyl‐1‐yl)borate}, to obtain the η²‐dithiocarbamate η¹‐pyrimidine complex [Pd(PPh₃)(η¹‐C₄H₃N₂)(η²‐S₂CNC₄H₈)], 4 and η²‐Tp η¹‐pyrimidine complex [Pd(PPh₃)(η¹‐C₄H₃N₂)(η²‐Tp)], 5 , respectively. Complexes 4 and 5 are characterized by X‐ray diffraction analyses.     

一个新颖镍配位阳离子修饰的还原型钼磷酸盐：Ni[Mo6O12(OH)3(PO4)(HPO4)3]2][Ni(H2O)2][Ni(H2O)(bipy)2]4·5H2O

水热合成并通过红外、热重、单晶X-射线衍射表征了一个新颖镍配位阳离子修饰的还原型钼磷酸盐,Ni[Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃]₂][Ni(H₂O)₂][Ni(H₂O)(bipy)₂]₄·5H₂O。单晶X-射线衍射研究表明,两个{Mo₆P₄}簇单元通过一个镍离子连接形成一个Ni[Mo₆P₄]₂二聚结构单元,其进一步和其他的镍配位阳离子连接成钼磷酸盐一维链状结构。在H₂O₂存在下的液－固体系中,使用该化合物催化氧化苯甲醛的探针反应结果表明,该化合物具有较高的催化氧化活性。     

Synthesis and Characterization of the Mixed‐Linker Copper(II) Coordination Polymer [Cu(HO3PC6H4SO3)(C10N2H8)]·H2O

A new copper(II) phosphonatobenzenesulfonate incorporating 4,4′‐bipyridine (4,4′‐bipy) as auxiliary ligand has been discovered through systematic high‐throughput (HT) screening of the system Cu(NO₃)₂·3H₂O/H₂O₃PC₆H₄SO₃H/4,4′‐bipy using different solvents. The hydrothermal synthesis of [Cu(HO₃PC₆H₄SO₃)(C₁₀H₈N₂)]·H₂O ( 1 ) was further optimized by screening various copper(II) salts. The crystal structure of 1 was determined by single‐crystal X‐ray diffraction and unveiled the presence of isolated sixfold coordinated Jahn–Teller‐distorted Cu²⁺ ions. The isolated CuN₂O₄ octahedra are interconnected by phosphonate and sulfonate groups to form chains along the c‐axis. The organic groups, namely phenyl rings and 4,4′‐bipy molecules cross‐link the chains into a three‐dimensional framework. Water molecules are found in the narrow voids in the structure which are held by weak hydrogen bonds. Upon dehydration, the structure of 1 undergoes a phase transition, which was confirmed by TG measurements and temperature dependent X‐ray powder diffraction. The new structure of 1‐h was refined with Rietveld methods. Detailed inspection of the structure revealed the directional switching of the Jahn–Teller distortion upon de/rehydration. Weak ferro‐/ferrimagnetic interactions were observed by magnetic investigations of 1 , which switch to antiferromagnetic below 3.5 K. Compounds 1 and 1‐h are further characterized by thermogravimetric and elemental analysis as well as IR spectroscopy.     

Comparison of two polymeric transition metal complexes with 1,4‐benzenedicarboxylate ions as bridging ligands, [Co(C8H4O4)(C12H8N2)(H2O)] and [Cu(C8H4O4)(C10H9N3)]·H2O

The title complexes, catena‐poly[[aqua(1,10‐phenanthroline‐κ²N,N′)­cobalt(II)]‐μ‐benzene‐1,4‐di­carboxyl­ato‐κ²O¹:O⁴], [Co(C₈H₄O₄)(C₁₂H₈N₂)(H₂O)], (I), and catena‐poly[[[(di‐2‐pyridyl‐κN‐amine)copper(II)]‐μ‐benzene‐1,4‐di­carboxyl­ato‐κ⁴O¹,O^1′:O⁴,O^4′] hydrate], [Cu(C₈H₄O₄)(C₁₀H₉N₃)]·H₂O, (II), take the form of zigzag chains, with the 1,4‐benzene­di­carboxyl­ate ion acting as an amphimonodentate ligand in (I) and a bis‐bidentate ligand in (II). The Co^II ion in (I) is five‐coordinate and has a distorted trigonal–bipyramidal geometry. The Cu^II ion in (II) is in a very distorted octahedral 4+2 environment, with the octahedron elongated along the trans O—Cu—O bonds and with a trans O—Cu—O angle of only 137.22 (8)°.     

Synthese verbrückter binuklearer Titanocenverbindungen – Kristallstruktur von Cl2Ti[(C5H4)(C5H4)(Me)Si–Si(Me)(C5H4)(C5H4)]TiCl2 · PhMe

Synthesis of Bridged Binuclear Titanocene Compounds – Crystal Structure of Cl₂Ti[(C₅H₄)(C₅H₄)(Me)Si–Si(Me)(C₅H₄)(C₅H₄)]TiCl₂ · PhMe Starting from Cp₂(Me)Si–Si(Me)Cp₂ 1 the complexes X₂Ti[(C₅H₄)(C₅H₄)(Me)Si–Si(Me)(C₅H₄)(C₅H₄)]TiX₂ (X = Cl ( 2 a ); X = Me ( 3 )) were synthesized. The compounds were characterized by means of their ¹H‐ and ¹³C‐n.m.r. and MS‐spectra. The crystal structure of 2 a · PhMe was determined.     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

Zinc(II) and Cadmium(II) Complexes of the 3‐(2‐Pyridyl)‐5,6‐diphenyl‐1,2,4‐triazine (PDPT) Ligand,Structural Studies of [Zn(PDPT)2Cl(ClO4)] and [Cd(PDPT)2(NO3)(ClO4)]

Two new mixed‐anion zinc(II) and cadmium(II) complexes of 3‐(2‐pyridyl)‐5,6‐diphenyl‐1,2,4‐triazine (PDPT) ligand, [Zn(PDPT)₂Cl(ClO₄)] and [Cd(PDPT)₂(NO₃)(ClO₄)], have been synthesized and characterized by elemental analysis, IR‐ and ¹H NMR spectroscopy. The single crystal X‐ray analyses show that the coordination number in these complexes is six with four N‐donor atoms from two “PDPT” ligand and two of the anionic ligands, ZnN₄ClO_perchlorate, CdN₄O_nitrateO_perchlorate. Self‐assembly of these compounds in the solid state via π–π‐stacking interactions is discussed.     

Selten‐Erd‐Metall‐Koordinationspolymere: Synthese und Kristallstrukturen von fünf neuen Adipinaten, [M2(Adi)3(H2O)4](AdiH2)(H2O)4 (M = La,Nd), [Er(Adi)(H2O)5]Cl(H2O) und [M(Adi)(H2O)5](NO3)(H2O) (M = Gd,Er)

Rare‐Earth‐Metal Coordination Polymers: Synthesis and Crystal Structures of Five New Adipinates, [M₂(Adi)₃(H₂O)₄](AdiH₂)(H₂O)₄ (M = La, Nd), [Er(Adi)(H₂O)₅]Cl(H₂O) and [M(Adi)(H₂O)₅](NO₃)(H₂O) (M = Gd, Er) The new rare‐earth compounds [M₂(Adi)₃(H₂O)₄](AdiH₂)(H₂O)₄ (M = La ( 1 ), Nd ( 2 )), [Er(Adi)(H₂O)₅]Cl(H₂O) ( 3 ) and [M(Adi)(H₂O)₅](NO₃)(H₂O) (M = Gd ( 4 ), Er ( 5 )) were obtained from the reaction of adipinic acid with La(OH)₃·xH₂O, Nd₂O₃, ErCl₃·6H₂O, Gd(NO)₃·xH₂O and Er₂O₃, respectively. Their crystal structures were determined by single‐crystal X‐ray diffraction. The coordination polymers [M₂(Adi)₃(H₂O)₄](AdiH₂)(H₂O)₄ crystallize in the triclinic space group (no. 2) with a = 875.4(1), b = 1000.4(2), c = 1179.0(2) pm, α = 74.70(1), β = 69.85(1), γ = 86.18(2)° and Z = 1 (crystal data for M = La, ( 1 )). The quasi‐isostructural compounds [Er(Adi)(H₂O)₅]Cl(H₂O) ( 3 ) and [M(Adi)(H₂O)₅](NO₃)(H₂O) (M = Gd ( 4 ), Er ( 5 )) crystallize with monoclinic symmetry, space group C2/c (no. 15) with lattice parameters of a = 1231.5(1), b = 1532.6(1), c = 895.4(1) pm, β = 123.44(1)° and Z = 4 (crystal data for ( 3 )). The rare‐earth cations have the coordination numbers 10 ( 1 , 2 ) and 9 ( 3 , 4 and 5 ), respectively. The compounds [M₂(Adi)₃(H₂O)₄](AdiH₂)(H₂O)₄ are constructed of infinite chains of edge‐sharig [MO₈(H₂O)₂] polyhedra that are cross‐linked by adipinic acid molecules to form framework structures. In [Er(Adi)(H₂O)₅]Cl(H₂O) ( 3 ) and [M(Adi)(H₂O)₅](NO₃)(H₂O) (M = Gd ( 4 ), Er ( 5 )) the central cations are bridged by adipinic acid molecules in a bidentate‐chelating manner to positively charged zigzag chains. Between these the counter ions and crystal water molecules are incorporated.     

Synthesis and Crystal Structures of the Molybdenum(II) Complexes with the N,N‐dimethylthiocarbamoyl Containing Ligand: Crystal Structures of [Mo(CO)2(η2‐S2COEt)(η2‐SCNMe2)(PPh3)] and [Mo(CO)2(η2‐S2CNC4H8)(η2‐SCNMe2)(PPh3)]

The reaction of the thiocarbamoyl‐molybdenum complex [Mo(CO)₂(η²‐SCNMe₂)(PPh₃)₂Cl] 1 , with EtOCS2K and C4H8NCS2NH4 in dichloromethane at room temperature yielded the seven coordinated ethyldithiocarbonate thiocarbamoyl‐molybdenum complex [Mo(CO)₂(η²‐S₂COEt)(η²‐SCNMe₂)(PPh₃)] 2 , and the dithiocarbamate thiocarbamoyl‐molybdenum complex [Mo(CO)₂(η²‐S₂CNC₄H₈)(η²‐SCNMe₂)(PPh₃)] 3 . The geometry around the metal atom of compounds 2 and 3 are capped octahedrons as revealed by X‐ray diffraction analyses. The thiocarbamoyl and ethyldithiocarbonate or pyrrolidinyldithiocarbamate ligands coordinate to the molybdenum metal center through the carbon and sulfur and two sulfur atoms, respectively. Structure parameters, NMR, IR and Mass spectra are in agreement with the crystal chemistry of the two compounds.     

Synthesis and Crystal Structure of Europium(II) Tartrate Tetrahydrate, [Eu(C4H4O6)(H2O)2](H2O)2

Single crystals of [Eu(C₄H₄O₆)(H₂O)₂](H₂O)₂ were obtained from the combination of solutions of EuCl₂, previously obtained by electrolysis of an aqueous solution of EuCl₃, and tartraric acid, neutralized by LiOH. The crystal structure (orthorhombic, P2₁2₁2₁, Z = 4, a = 948.9(1), b = 954.6(1), c = 1098.4(1) pm; R(F) = 0.0242 and R_w(F²) = 0.0585 for I > 2σ(I); R(F) = 0.0256 and R_w(F²) = 0.0592 for all data) is isotypic with [Ca(C₄H₄O₆)(H₂O)₂](H₂O)₂ and [Sr(C₄H₄O₆)(H₂O)₂](H₂O)₂ exhibiting a three‐dimensional structure. The divalent cations (Eu²⁺, Ca²⁺, Sr²⁺) are eight‐coordinate by oxygen atoms that originate from carboxylate and hydroxyl groups of the tartraric dianion and two of the four water molecules.     

Synthesis,Structure, and Reactivity of a Tetranuclear Cerium(IV) Oxo Cluster Supported by the Kläui Tripodal Ligand [Co(η5‐C5H5){P(O)(OEt)2}3]−

A tetranuclear Ce^IV oxo cluster compound containing the Kläui tripodal ligand [Co(η⁵‐C₅H₅){P(O)(OEt)₂}₃]^? (L_OEt^?) has been synthesized and its reactions with H₂O₂, CO₂, NO, and Brønsted acids have been studied. The treatment of [Ce(L_OEt)(NO₃)₃] with Et₄NOH in acetonitrile afforded the tetranuclear Ce^IV oxo cluster [Ce₄(L_OEt)₄O₇H₂] ( 1 ) containing an adamantane‐like {Ce₄(μ₂‐O)₆} core with a μ₄‐oxo ligand at the center. The reaction of 1 with H₂O₂ resulted in the formation of the peroxo cluster [Ce₄(L_OEt)₄(μ₄‐O)(μ₂‐O₂)₄(μ₂‐OH)₂] ( 2 ). The treatment of 1 with CO₂ and NO led to isolation of [Ce(L_OEt)₂(CO₃)] and [Ce(L_OEt)(NO₃)₃], respectively. The protonation of 1 with HCl, ROH (R=2,4,6‐trichlorophenyl), and Ph₃SiOH yielded [Ce(L_OEt)Cl₃] ( 3 ), [Ce(L_OEt)(OR)₃] ( 4 ), and [Ce(L_OEt)(OSiPh₃)₃] ( 5 ), respectively. The chloride ligands in 3 are labile and can be abstracted by silver(I) salts. The treatment of 3 with AgOTs (OTs^?=tosylate) and Ag₂O afforded [Ce(L_OEt)(OTs)₃] ( 6 ) and 1 , respectively. The electrochemistry of the Ce‐L_OEt complexes has been studied by using cyclic voltammetry. The crystal structures of complexes 1 – 5 have been determined.