X‐ray crystal of diprotonated tetra‐(2‐pyridyl)pyrazine (H2TPPZ), aqua Fe3+‐phen crystal and new lanthanide complexes of TPPZ and their biochemical studies

New complexes derived from M³⁺ salts with polyazine as monometallic such as [Fe (TPPZ)Cl₃].½H₂O (1) , [Cr (TPPZ)₂Cl₂]Cl.2EtOH (2) , [La (TPPZ)(NO₃)₂(H₂O)₂]NO₃.H₂O (3) in addition to [Fe (Phen)₃]3Cl.7H₂O (4) were isolated. Three bimetallic, [H₂TPPZ][(AuCl₄)₂]. H₂O (5) , [Ce₂(TPPZ)EtOH (NO₃)₃]3NO₃ (6) and [Nd₂TPPZCl₂(H₂O)₄]4Cl.CHCl₃. 4H₂O (7) and mixed ligand complexes, [Fe (TPPZ)(Phen)₂]Cl₃ (8) , [Fe (TPPZ) (Phen)₂][TPPZCl₃] (9) , [La₂(TPPZ)(Phen)₂(EtOH)₂]6Cl.CHCl₃.EtOH.H₂O (10) and [Nd₂(TPPZ)(Phen)Cl₄]2Cl.3H₂O (11) were synthesized and characterized. Crystal data of (4) is tetragonal, I4₁/a, a = b 35.951 (3) Å, c = 11.9055 (8) Å, α = 80.201 (2)° β = 78.846 (2)°, γ = 89.687 (2)° V = 741.06 (5)ų, Z = 1 while triclinic, P1, a = 7.3913 (3) Å, b = 9.7344 (4) Å, c = 10.6577 (4) Å, α = β = γ = 90°, V = 741.06 (5)ų and Z = 170 for (5) . Analyses, spectral and cyclic voltammetry studies indicate the bonding and the redox properties. Anticancer studies promised to be effective in lanthanides and some complexes were screened against antibacterial or antifungal.     

Aktivierung von Schwefelkohlenstoff an Trirutheniumclustern: Synthese und Kristallstruktur von [Ru3(CO)5(μ‐H)2(μ‐PCy2)(μ‐Ph2PCH2PPh2){μ‐η2‐PCy2C(S)}(μ3‐S)] und [Ru3(CO)5(CS)(μ‐H)(μ‐PtBu2)(μ‐PCy2)2(μ3‐S)]

Activation of Carbon Disulfide on Triruthenium Clusters: Synthesis and X‐Ray Crystal Structure Analysis of [Ru₃(CO)₅(μ‐H)₂(μ‐PCy₂)(μ‐Ph₂PCH₂PPh₂){μ‐η²‐PCy₂C(S)}(μ₃‐S)] and [Ru₃(CO)₅(CS)(μ‐H)(μ‐P^tBu₂)(μ‐PCy₂)₂(μ₃‐S)] [Ru₃(CO)₆(μ‐H)₂(μ‐PCy₂)₂(μ‐dppm)] ( 1 ) (dppm = Ph₂PCH₂PPh₂) reacts under mild conditions with CS₂ and yields by oxidative decarbonylation and insertion of CS into one phosphido bridge the opened 50 VE‐cluster [Ru₃(CO)₅(μ‐H)₂(μ‐PCy₂)(μ‐dppm){μ‐η²‐PCy₂C(S)}(μ₃‐S)] ( 2 ) with only two M–M bonds. The compound 2 crystallizes in the triclinic space group P 1 with a = 19.093(3), b = 12.2883(12), c = 20.098(3) Å; α = 84.65(3), β = 77.21(3), γ = 81.87(3)° and V = 2790.7(11) ų. The reaction of [Ru₃(CO)₇(μ‐H)(μ‐P^tBu₂)(μ‐PCy₂)₂] ( 3 ) with CS₂ in refluxing toluene affords the 50 VE‐cluster [Ru₃(CO)₅(CS)(μ‐H)(μ‐P^tBu₂)(μ‐PCy₂)₂(μ₃‐S)] ( 4 ). The compound cristallizes in the monoclinic space group P 2₁/a with a = 19.093(3), b = 12.2883(12), c = 20.098(3) Å; β = 104.223(16)° and V = 4570.9(10) ų. Although in the solid state structure one elongated Ru–Ru bond has been found the complex 4 can be considered by means of the ³¹P‐NMR data as an electron‐rich metal cluster.     

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.     

[Hg2(μ‐bpe)(μ‐OAc)2(μ‐SCN)2]n,a New Two‐Dimensional Coordination Polymer Involving Three Simultaneously Bridging Ligands: 1,2‐Bis(4‐pyridyle)ethene,Acetate, and Thiocyanate

A new mercury(II) complex of 1,2‐bis(4‐pyridyle)ethene (bpe) with anionic acetate and thiocyanate ligands has been synthesized and characterized by elemental analysis, IR, ¹H NMR and ¹³C NMR spectroscopy. The single crystal X‐ray analysis shows that the complex is a two‐dimensional polymer with simultaneously bridging 1,2‐bis(4‐pyridyle)ethane, acetate and thiocyanate ligands and basic repeating dimeric [Hg₂(μ‐bpe)(μ‐OAc)₂(μ‐SCN)₂] units. The two‐dimensional system forms a three‐dimensional network by packing via π‐π stacking interactions.     

Synthesis and Crystal Structures of the Molybdenum(II) Complexes with the N,N‐dimethylthiocarbamoyl Containing Ligand: Crystal Structures of β [Mo(CO)2{η2‐S2P(OEt)2}(η2‐SCNMe2)(PPh3)] and [Mo(CO)2(η3‐Tp)(η2‐SCNMe2)(PPh3)]

Reactions of the thiocarbamoyl‐molybdenum complex [Mo(CO)₂(η²‐SCNMe₂)(PPh₃)₂Cl] 1 , and ammonium diethyldithiophosphate, NH₄S₂P(OEt)₂, and potassium tris(pyrazoyl‐1‐yl)borate, KTp, in dichloromethane at room temperature yielded the seven coordinated diethyldithiophosphate thiocarbamoyl‐molybdenum complexe [Mo(CO)₂{η²‐S₂P(OEt)₂}(η²‐SCNMe₂)(PPh₃)] β‐3 , and tris(pyrazoyl‐1‐yl)borate thiocabamoyl‐molybdenum complex [Mo(CO)₂(η³‐Tp)(η²‐SCNMe₂)(PPh₃)] 4 , respectively. The geometry around the metal atom of compounds β‐3 and 4 are capped octahedrons. The α‐ and β‐isomers are defined to the dithio‐ligand and one of the carbonyl ligands in the trans position in former and two carbonyl ligands in the trans position in later. The thiocabamoyl and diethyldithiophosphate or tris(pyrazoyl‐1‐yl)borate ligands coordinate to the molybdenum metal center through the carbon and sulfur and two sulfur atoms, or three nitrogen atoms, respectively. Complexes β‐3 and 4 are characterized by X‐ray diffraction analyses.     

Heterodinukleare Komplexe: Synthese und Kristallstrukturen von [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)], [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)]

Heterobinuclear Complexes: Synthesis and X‐ray Crystal Structures of [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)], [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)], and [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] [Ru₃Rh(CO)₇(μ₃‐H)(μ‐P^tBu₂)₂(^tBu₂PH)(μ‐Cl)₂] ( 2 ) yields by cluster degradation under CO pressure as main product the heterobinuclear complex [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)] ( 4 ). The compound crystallizes in the orthorhombic space group Pcab with a = 15.6802(15), b = 28.953(3), c = 11.8419(19) Å and V = 5376.2(11) ų. The reaction of 4 with dppm (Ph₂PCH₂PPh₂) in THF at room temperature affords in good yields [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐dppm)] ( 7 ). 7 crystallizes in the triclinic space group P 1 with a = 9.7503(19), b = 13.399(3), c = 15.823(3) Å and V = 1854.6 ų. Moreover single crystals of [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 9 ) could be obtained and the single‐crystal X‐ray structure analysis revealed that 9 crystallizes in the monoclinic space group P2₁/a with a = 11.611(2), b = 13.333(2), c = 18.186(3) Å and V = 2693.0(8) ų.     

Synthesis and Characterization of the First Doubly‐bridged N,N‐dimethylthiocarbamoyl Metal Complex: Crystal Structure of [Mo(Cl)(CO)2(PPh3)]2(η1:η2:μ‐SCNMe2)2

The first doubly‐bridged thiocarbamoyl metal complex [Mo(Cl)(CO)₂(PPh₃)]₂(η¹:η²:μ‐SCNMe₂)₂ ( 2 ) was formed from stirring [Mo(CO)₂(η²‐SCNMe₂)(PPh₃)₂Cl] ( 1 ) in dichloromethane at room temperature. Complex 2 is a dimer with each thiocarbamoyl unit coordinating through sulfur and carbon to one metal center and bridging both metals through sulfur. Complex 2 is characterized by X‐ray diffraction analysis.     

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.     

Aktivierung von Schwefelkohlenstoff an Trirutheniumclustern: Synthese und Kristallstruktur von [Ru3(CO)4(μ‐PCy2)2(μ‐Ph2PCH2PPh2)(μ3‐S){μ3‐η2‐CSC(S)S}]

Activation of Carbon Disulfide on Triruthenium Clusters: Synthesis and X‐Ray Crystal Structure Analysis of [Ru₃(CO)₄(μ‐PCy₂)₂(μ‐Ph₂PCH₂PPh₂)(μ₃‐S){μ₃‐η²‐CSC(S)S}] [Ru₃(CO)₄(μ‐H)₃(μ‐PCy₂)₃(μ‐dppm)] ( 2 ) (dppm = Ph₂PCH₂PPh₂) reacts with CS₂ at room temperature and yields the open 50 valence electron cluster [Ru₃(CO)₄(μ‐PCy₂)₂(μ‐dppm)(μ₃‐S){μ₃‐η²‐CSC(S)S}] ( 3 ) containing the unusual μ₃‐η²‐C₂S₃ mercaptocarbyne ligand. Compound 3 was characterized by single crystal X‐ray structure analysis.     

Molybdän‐ und Wolfram‐Komplexe mit MNS‐Sequenzen. Die Kristallstrukturen von [MoCl3(N3S2)(1,4‐Dioxan)2] und [Mo2Cl2(μ‐NSN)2(μ‐O)(NCMe3)(OCMe3)2]2

Molybdenum and Tungsten Complexes with MNS Sequences. Crystal Structures of [MoCl₃(N₃S₂)(1,4‐dioxane)₂] and [Mo₂Cl₂(μ‐NSN)₂(μ‐O)(NCMe₃)(OCMe₃)₂]₂ The cyclo‐thiazeno complexes [Cl₃MNSNSN]₂ of molybdenum and tungsten react with 1,4‐dioxane in dichloromethane suspension to give the binuclear donor‐acceptor complexes [μ‐(1,4‐dioxane){MCl₃(N₃S₂)}₂] which are characterized by IR spectroscopy. With excess 1,4‐dioxane the molybdenum compound forms the complex [MoCl₃(N₃S₂)(1,4‐dioxane)₂] in which, according to the crystal structure determination, one of the dioxane molecules coordinates at the molybdenum atom, the other one at one of the sulfur atoms of the cyclo‐thiazeno ring. The μ‐(NSN^2–) complex [Mo₂Cl₂(μ‐NSN)₂(μ‐O)(NCMe₃)(OCMe₃)₂]₂ has been obtained by the reaction of [MoN(OCMe₃)₃] with trithiazyle chloride in carbontetrachloride solution. According to the crystal structure determination this compound forms centrosymmetric dimeric molecules via two of the nitrogen atoms of two of the μ‐(NSN) groups to give a Mo₂N₂ fourmembered ring. [MoCl₃(N₃S₂)(1,4‐dioxane)₂]: Space group P2₁/c, Z = 4, lattice dimensions at –70 °C: a = 1522.9(2); b = 990.3(1); c = 1161.7(1) pm; β = 106.31(1)°, R₁ = 0.0317. [Mo₂Cl₂(μ‐NSN)₂(μ‐O)(NCMe₃)(OCMe₃)₂]₂ · 4 CCl₄: Space group P2₁/c, Z = 2, lattice dimensions at –83 °C: a = 1216.7(1); b = 2193.1(2); c = 1321.8(1) pm; β = 98.23(1)°; R₁ = 0.0507.     

Koordinativ ungesättigte Dieisenkomplexe: Synthese und Kristallstrukturen von [Fe2(CO)4(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [Fe2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)]

Coordinatively Unsaturated Diiron Complexes: Synthesis and Crystal Structures of [Fe₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] and [Fe₂(CO)₄(μ‐CH₂)(μ‐H)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] [Fe₂(μ‐CO)(CO)₆(μ‐H)(μ‐P^tBu₂)] ( 1 ) reacts spontaneously with dppm (dppm = Ph₂PCH₂PPh₂) to give [Fe₂(μ‐CO)(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 2 c ). By thermolysis or photolysis, 2 c loses very easily one carbonyl ligand and yields the corresponding electronically and coordinatively unsaturated complex [Fe₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 3 ). 3 exhibits a Fe–Fe double bond which could be confirmed by the addition of methylene to the corresponding dimetallacyclopropane [Fe₂(CO)₄(μ‐CH₂)(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 4 ). The reaction of 1 with dppe (Ph₂PC₂H₄PPh₂) affords [Fe₂(μ‐CO)(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppe)] ( 5 ). In contrast to the thermolysis of 2 c , yielding 3 , the heating of 5 in toluene leads rapidly to complete decomposition. The reaction of 1 with PPh₃ yields [Fe₂(CO)₆(H)(μ‐P^tBu₂)(PPh₃)] ( 6 a ), while with ^tBu₂PH the compound [Fe₂(μ‐CO)(CO)₅(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 6 b ) is formed. The thermolysis of 6 b affords [Fe₂(CO)₅(μ‐P^tBu₂)₂] and the degradation products [Fe(CO)₃(^tBu₂PH)₂] and [Fe(CO)₄(^tBu₂PH)]. The molecular structures of 3 , 4 and 6 b were determined by X‐ray crystal structure analyses.     

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.     

Solvothermal Synthesis and Crystal Structures of Two Manganese Complexes [Mn(II)(acac−)2(4,4′‐bipy)]n (bipy=4,4′‐bipyridine) and [Mn(III)(acac−)3]·4CO(NH2)2

Two special manganese complexes [Mn(II)(acac^?)₂(4,4′‐bipy)]_n (bipy=4,4′‐bipyridine) (complex 1 ) and [Mn(III)(acac^?)₃]·4CO(NH₂)₂ (acacH=acetylacetone) (complex 2 ) were synthesized in the same strategy by solvothermal method. Single crystal X‐ray diffraction revealed the complex 1 consists of one‐dimensional infinite coordination chain, with the manganese centers bridged by 4,4′‐bipy. And free carbamides of complex 2 connect with each other through the hydrogen bonds to form a 14‐membered carbamide ring and a zig‐zag plane. Both enantiomers of Mn(III)(acac^?)₃ exist in the structure, forming a racemate. Furthermore, these enantiomers and those zig‐zag planes are linked with hydrogen bonds to form an unique spatial network.     

Direct Synthesis of PbO Nanoparticles From a Lead(II) Nano Coordination Polymer Precursor: Synthesis,Crystal Structure,and DFT Calculations of [Pb2(dmp)2(μ‐N3)2(μ‐ClO4)2]n with the First Pb2‐(μ‐ClO4)2 Unit

Nanostructures of a new coordination polymer of divalent lead with the ligand 2, 9‐dimethyl‐1, 10‐phenanthroline (dmp) containing the first Pb₂‐(μ‐ClO₄)₂ motif, [Pb₂(dmp)₂(μ‐N₃)₂(μ‐ClO₄)₂]_n ( 1 ), was synthesized by a sonochemical method that produces the coordination polymers at nano size. The new nanostructure was characterized by scanning electron microscopy, X‐ray powder diffraction, IR, ¹H NMR and ¹³C NMR spectroscopy, and elemental analysis. Compound 1 was structurally characterized by single‐crystal X‐ray diffraction and the single‐crystal X‐ray data shows that the coordination number of Pb^II ions is six, (PbN₄O₂), with two N‐donor atoms from aza‐aromatic base ligands and four O‐donors from two perchlorate anions and two N‐donors from two azide anions. It has a “stereo‐chemically active” electron lone pair, and the coordination sphere is hemidirected. The supramolecular features in these complexes are guided and controlled by weak directional intermolecular interactions. The chains interact with each other through π–π stacking interactions creating a 3D framework. The structure of the title complex was optimized by density functional theory calculations. Calculated structural parameters and IR spectra for the title complex are in agreement with the crystal structure. The PbO nanoparticles were obtained by thermolysis of 1 at 180 °C with oleic acid as a surfactant. The average diameter of the nanoparticles was estimated by the Scherrer equation to be 23 nm. The morphology and size of the prepared PbO samples were further observed using SEM.     

Sulfur‐Assisted Intermolecular Triphenylphosphine Dissociation of Thiocarbamoyl Ligand in Platinum(II). X‐ray Structure of Complex [Pt(PPh3)2(η1‐SCNMe2)(Cl)]

Treatment of Pt(PPh₃)₄ with N,N‐dimethylthiocarbamoyl chloride, Me₂NC(=S)Cl, in dichloromethane at ?20 °C processes the oxidative addition reaction to produce platinum complex [Pt(PPh₃)₂(η¹‐SCNMe₂)(Cl)], 2 with releasing two triphenylphosphine molecules. The ³¹P{¹H} NMR spectra of complex 2 shows the dissociation of the triphenylphosphine ligand to form diplatinum complex [Pt(PPh₃)Cl]₂(μ,η²‐SCNMe₂)₂, 3 in which the two SCNMe₂ ligands coordinated through carbon to one metal center and bridging the other metal through sulfur. Complex 2 is characterized by X‐ray diffraction analysis.     

{[Mn2(μ3‐Tda)2(μ‐H2O)(H2O)2(bipy)]·DMF}n – a 2D Manganese(II) Coordination Polymer involving Six‐membered Binuclear Metallacycle Nodes

The single crystal X‐ray analysis of a novel thiophene‐2,5‐dicarboxylic acid (H₂Tda) Manganese(II) coordination polymer, {Mn₂(μ₃‐Tda)₂(μ‐H₂O)(H₂O)₂(bipy)]·DMF}_n, shows two different types of Mn²⁺‐ions with environment of Mn1O₆ and Mn2O₄N₂, and the complex is a two‐dimensional polymer as a result of bridging (Tda)^2? ligands and by connecting the carboxylate‐ and water‐bridged {Mn₂(μ‐Tda)₂(μ‐H₂O)} nodes.     

Koordinativ ungesättigte Dirutheniumkomplexe: Synthese und Kristallstrukturen von [Ru2(CO)4(μ‐H)(μ‐S)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [Ru2(CO)4(μ‐X)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (X = Cl,S2CH)

Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐Ray Crystal Structures of [Ru₂(CO)₄(μ‐H)(μ‐S)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)], [Ru₂(CO)₄(μ‐X)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] (X = Cl, S₂CH) [Ru₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 1 ) reacts in benzene with elemental sulfur to the addition product [Ru₂(CO)₄(μ‐H)(μ‐S)(μ‐P^tBu₂)(μ‐dppm)] ( 2 ) (dppm = Ph₂PCH₂PPh₂). 2 is also obtained by reaction of 1 with ethylene sulfide. The reaction of 1 with carbon disulfide yields with insertion of the CS₂ into the Ru₂(μ‐H) bridge the dithioformato complex [Ru₂(CO)₄(μ‐S₂CH)(μ‐P^tBu₂)(μ‐dppm)] ( 3 ). Furthermore, 1 reacts with [NO][BF₄] to the complex salt [Ru₂(CO)₄(μ‐NO)(μ‐H)(μ‐P^tBu₂)(μ‐dppm)][BF₄] ( 4 ), and reaction of 1 with CCl₄ or CHCl₃ affords spontaneously [Ru₂(CO)₄(μ‐Cl)(μ‐P^tBu₂)(μ‐dppm)] ( 5 ) in nearly quantitative yield. The molecular structures of 2 , 3 and 5 were confirmed by crystal structure analyses.     

A three‐dimensional coordination polymer based on the Zn4(μ3‐OH)2 unit: poly[[(μ4‐benzene‐1,4‐dicarboxylato)bis(μ3‐benzene‐1,4‐dicarboxylato)bis(μ3‐hydroxido)bis(1,10‐phenanthroline‐5,6‐dione)tetrazinc] dihydrate]

The title compound, {[Zn₄(C₈H₄O₄)₃(OH)₂(C₁₂H₆N₂O₂)₂]·2H₂O}_n, has been prepared hydrothermally by the reaction of Zn(NO₃)₂·6H₂O with benzene‐1,4‐dicarboxylic acid (H₂bdc) and 1,10‐phenanthroline‐5,6‐dione (pdon) in H₂O. In the crystal structure, a tetranuclear Zn₄(OH)₂ fragment is located on a crystallographic inversion centre which relates two subunits, each containing a [ZnN₂O₄] octahedron and a [ZnO₄] tetrahedron bridged by a μ₃‐OH group. The pdon ligand chelates to zinc through its two N atoms to form part of the [ZnN₂O₄] octahedron. The two crystallographically independent bdc²⁻ ligands are fully deprotonated and adopt μ₃‐κO:κO′:κO′′ and μ₄‐κO:κO′:κO′′:κO′′′ coordination modes, bridging three or four Zn^II cations, respectively, from two Zn₄(OH)₂ units. The Zn₄(OH)₂ fragment connects six neighbouring tetranuclear units through four μ₃‐bdc²⁻ and two μ₄‐bdc²⁻ ligands, forming a three‐dimensional framework with uninodal 6‐connected α‐Po topology, in which the tetranuclear Zn₄(OH)₂ units are considered as 6‐connected nodes and the bdc²⁻ ligands act as linkers. The uncoordinated water molecules are located on opposite sides of the Zn₄(OH)₂ unit and are connected to it through hydrogen‐bonding interactions involving hydroxide and carboxylate groups. The structure is further stabilized by extensive π–π interactions between the pdon and μ₄‐bdc²⁻ ligands.     

Synthesis,Spectroscopy, and Structures of Mono‐ and Dinuclear Copper(I) Halide Complexes with 1,3‐Imidazolidine‐2‐thiones

Copper(I) halides with triphenyl phosphine and imidaozlidine‐2‐thiones (L ‐NMe, L ‐NEt, and L ‐NPh) in acetonitrile/methanol (or dichloromethane) yielded copper(I) mixed‐ligand complexes: mononuclear, namely, [CuCl(κ¹‐S‐L ‐NMe)(PPh₃)₂] ( 1 ), [CuBr(κ¹‐S‐L ‐NMe)(PPh₃)₂] ( 2 ), [CuBr(κ¹‐S‐L ‐NEt)(PPh₃)₂] ( 5 ), [CuI(κ¹‐S‐L ‐NEt)(PPh₃)₂] ( 6 ), [CuCl(κ¹‐S‐L ‐NPh)(PPh₃)₂] ( 7 ), and [CuBr(κ¹‐S‐L ‐NPh)(PPh₃)₂] ( 8 ), and dinuclear, [Cu₂(κ¹‐I)₂(μ‐S‐L ‐NMe)₂(PPh₃)₂] ( 3 ) and [Cu₂(μ‐Cl)₂(κ¹‐S‐L ‐NEt)₂(PPh₃)₂] ( 4 ). All complexes were characterized with analytical data, IR and NMR spectroscopy, and X‐ray crystallography. Complexes 2 – 4 , 7 , and 8 each formed crystals in the triclinic system with P$\bar{1}$ space group, whereas complexes 1 , 5 , and 6 crystallized in the monoclinic crystal system with space groups P2₁/c, C2/c, and P2₁/n, respectively. Complex 2 has shown two independent molecules, [(CuBr(κ¹‐S‐L ‐NMe)(PPh₃)₂] and [CuBr(PPh₃)₂] in the unit cell. For X = Cl, the thio‐ligand bonded to metal as terminal in complex 4 , whereas for X = I it is sulfur‐bridged in complex 3 .     

2‐Amino‐5‐(2‐pyridyl)‐thiadiazole as Bidentate Ligand

The amino substituted bidentate chelating ligand 2‐amino‐5‐(2‐pyridyl)‐1,3,4‐thiadiazole (H₂ L ) was used to prepare 3:1‐type coordination compounds of iron(II), cobalt(II) and nickel(II). In the iron(II) perchlorate complex [Fe^II(H₂ L )₃](ClO₄)₂·0.6MeOH·0.9H₂O a 1:1 mixture of mer and fac isomers is present whereas [Fe^II(H₂ L )₃](BF₄)₂·MeOH·H₂O, [Co^II(H₂ L )₃](ClO₄)₂·2H₂O and [Ni^II(H₂ L )₃](ClO₄)₂·MeOH·H₂O feature merely mer derivatives. Moessbauer spectroscopy and variable temperature magnetic measurements revealed the [Fe^II(H₂ L )₃]²⁺ complex core to exist in the low‐spin state, whereas the [Co^II(H₂ L )₃]²⁺ complex core resides in its high‐spin state, even at very low temperatures.