Synthesis of the hydroxide cluster [Al13(μ3-OH)6(μ-OH)18(H2O)24]15+ from an aqueous solution

A scalable synthesis of the "flat" tridecameric inorganic cluster [Al(13)(μ(3)-OH)(6)(μ-OH)(18)(H(2)O)(24)](15+) has been realized by treating an aqueous aluminum nitrate solution with a zinc-metal powder at room temperature. Single crystals and polycrystalline samples are readily obtained in yields exceeding 55% relative to the starting reagent Al(NO(3))(3). Products have been characterized by X-ray diffraction and solid-state (27)Al MAS and MQMAS NMR.     

Synthesis and Structure of a Novel Mg6 Cluster Molecule Mg6(μ3-OH)2(μ3-Br)2(μ-Br)8(THF)8

A novel Mg₆ cluster molecule with the formula of Mg₆( ₃-OH)₂( ₃-Br)₂(-Br)₈(THF)₈ (1) has been isolated in 38% yield from a reaction of the Grignard reagent, 2-naphthyl-Mg-Br with BBr₃ in THF. The structure of 1, determined by a single-crystal X-ray diffraction analysis, contains two Mg₃ triangles linked together by two bridging bromide ligands. Within each Mg₃ triangle, one hydroxide and one bromide ligand function as triply bridging ligands capping both sides of the Mg₃ triangle. The coordination geometry around each Mg(II) ion is approximately octahedral. NMR studies revealed that compound 1 is highly fluxional in solution.     

Synthesis and crystal structure of a novel mercapto-organotin complex:[Et3NH][Ph2SnCl(μ2-SCH2COO-)]

A novel complex[Et₃NH][Ph₂SnCl(μ²-SCH₂COO-)],has been unexpectedly obtained by the reaction of Ph₃SnCl and HSCH₂COOH in 2:1 molar ratio in the presence of organic base Et₃N.     

Synthesis, properties, and crystal structure of the tin(IV) complex with N-(2-hydroxyethyl)ethylenediaminetriacetic acid [Sn(μ-Hedtra)(μ-OH)SnCl3(H2O)] · 3H2O

The binuclear tin(IV) complex with N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid (H₄Hedtra) is synthesized. The compound is characterized by elemental analysis, thermogravimetry, and IR spectroscopy. An X-ray diffraction analysis of complex Sn(μ-Hedtra)(μ-OH)SnCl₃(H₂O)] · 3H₂O (I) is carried out. Structure I is formed by the binuclear complexes and molecules of water of crystallization. One of the tin atoms coordinates six “active” sites Hedtra^4? (the alcohol branch is deprotonated and forms a bridge between two tin atoms) and the bridging hydroxo group. The polyhedron is a pentagonal bipyramid. The octahedral environment of the second tin atom is formed by two bridging oxygen atoms, three chlorine atoms (fac isomer), and a coordination water molecule.     

Synthesis and structure of the dimeric organo-antimony (V) imido complex [Ph3Sb(μ-NCH2CH2Ph)]2

The amine PhCH₂CH₂NH₂ undergoes dimetallation by [Ph₃Sb(NMe₂)₂] (1) under mild conditions to give the first structurally authenticated example of an organo-Sb(V) imido complex, [Ph₃Sb(μ-NCH₂CH₂Ph)]₂ (2).     

{Cp'Fe(μ-OH)}3]: the synthesis of a unique organometallic iron hydroxide

The synthesis of a novel trimeric iron(II) hydroxo complex stabilized by the sterically demanding 1,2,4-tri-tert-butyl-cyclopentadienyl ligand is reported. The high-spin iron(II) centres exhibit weak antiferromagnetic exchange coupling.     

Cleavage of 1,4-diphenylbuta-1,3-diyne on a ruthenium-cobalt cluster: Synthesis and molecular structure of Co2Ru3(μ4−C2Ph)(μ3−C2Ph)(μ-dppm)(μ-CO)2(CO)9

The reaction between Ru₃(₃-²-PhC₂C=CPh)(-dppm)(CO)₈ and Co₂(CO)₈ afforded dark red Co₂Ru₃(₄-C₂Ph)(₃-C₂Ph)(-dppm)(-CO)₂(CO)₉, shown by an X-ray structure determination to contain a strongly twisted Co₂Ru₃ bow-tie cluster (central Co), to which two PhC₂ units derived from cleavage of the original diyne are attached. One a these is strongly interacting with four metal atoms, the other being attached in the familiar ¹,2²-mode. The dppm ligand remains bridging two of the Ru atoms.     

Synthesis and Crystal Structure of FeCo_2(CO)_8(μ_3-S)〔P(OCH_2Ph)_3〕

1INTRODUCTIONBytreatingFeCo2(CO),(p,-S)withgroupVligands[L=PPh,,AsPh,,PBus",p(OEt),j,monosubstitutedderivativesFeCo2(CO),(p,-S)(L)havebeenobtained{1'2i.13C-NMRshowedthatthereplacementofCObyagroupVligandinFeCo,(CO),(p,-S)isatonecobaltatominthemonosubstitutedderivativet2).How-ever,thesubstitutedderivativeofFeCo,(CO),(p,-S)withP(OCH,Ph),hasnotbeenreportedanditscrystalstructurehasnotbeendetermined.WehavesynthesizedthetitlecompoundFeCo,(CO),(p,-S)[P(OCH,Ph),jandtestifiedth…     

Preparation of organozirconium aromatic compounds in mixed aqueous-organic solvents: X-ray structures of [Cp2ZrCl(μ2-O′,O′′C-C6H5)], [(CpZr)3(μ2-O′,O′′C-C6H3Cl2)3(μ3-OH)(μ2-OH)3](Cl2C6H3COO)2, and [(CpZr)3(μ2-O′,O′′C-C6H4Cl)3(μ3-OH)(μ2-OH)3]Cl2·CH2Cl2

A new and facile method is presented for the synthesis of zirconocene carboxylate compounds, in which zirconocene dichloride (Cp₂ZrCl₂) is dissolved in 1 M aqueous HCl solution and the requisite ligand is dissolved in an organic solvent. Five such compounds [Cp₂ZrCl(μ₂-O′,O′′C-C₆H₅)] (1), [Cp₂ZrCl(μ₂-O′,O′′C-C₆H₃Cl₂)] (2), [Cp₂Zr(μ₂-O′,O′′C-C₆H₃(OH)Cl)₂] (3), [Cp₂Zr(μ₂-O′,O′′C-C₆H₃(OH)(NO₂))₂] (4), and [Cp₂Zr(μ₂-O′,O′′C-C₆H(OH)Cl₃)₂] (5) have been obtained by this method. The effect of pH on the stability of Cp₂ZrCl₂ in 1 M HCl solution has been investigated by UV/vis spectrophotometry and ¹H NMR spectrometry. The results showed that the aqueous Cp₂ZrCl₂ solutions became less stable with increasing pH, liberating cyclopentadiene. Accordingly, at higher pH (～7), two trinuclear zirconium monocyclopentadienyl compounds, [(CpZr)₃(μ₂-O′,O′′C-C₆H₃Cl₂)₃(μ₃-OH)(μ₂-OH)₃](Cl₂C₆H₃COO)₂ (6) and [(CpZr)₃(μ₂-O′,O′′C-C₆H₄Cl)₃(μ₃-OH)(μ₂-OH)₃]Cl₂·CH₂Cl₂ (7), were obtained. All compounds 1–7 have been characterized by FT-IR, ¹H NMR spectra and elemental analysis. In all of the compounds, the aromatic acid acts as a bidentate ligand in coordinating to the zirconium; both chelating and bridging modes are observed. X-ray crystallographic studies on 1, 6, and 7 have revealed that the geometries at zirconium are distorted octahedral in 6 and 7, and distorted trigonal-bipyramidal in 1.     

Crystal structure of [Pd3(μ-OH)(μ-CH3COO)5]

The crystals of the [Pd₃(μ-OH)(μ-CH₃COO)₅] complex are obtained and characterized using powder and single crystal X-ray diffraction and IR spectroscopy. The crystal structure (a = 15.6942(6) Å, b = 11.7190(3) Å, c = 9.7871(3) Å, V = 1800.05(10) ų, space group Pna2₁, Z = 4) is formed from neutral trinuclear cyclic molecules of [Pd₃(μ-OH)(μ-CH₃COO)₅], in which the OH^? group, together with five CH₃COO^? anions, is a bridge ligand.     

Formation and Structure of [Al_(13)(μ_3-OH)_6(μ_2-OH)_6(μ_2-OH)_(12)(H_2O)_(24)]Cl_(15)·13H_2O

1 INTRODUCTION At present, the polyaluminium compounds are mainly studied by single-crystal X-ray diffraction method to obtain the components, structures and exis- tence forms of aluminium in hydrolysis system, and then hydrolysis courses and mechanisms of each hydrolytic polyaluminium cation could be further dis- closed[1～5]. Generally, the single crystals suitable for X-ray diffraction are obtained from the crystallization of polyaluminium cations into sulfates or selenates. Following …     

Synthesis and Molecular Structure of Tris(pentamethylphenyl)aluminum, (C6Me5)3Al, and the Magnesium Cluster [Mg6(μ3-OH)2(μ3-Br)2(μ2-Br)8(OEt2)8]

The synthesis and molecular structures of tris(pentamethylphenyl)aluminum, (C₆Me₅)₃Al, (I), and the magnesium cluster [Mg₆( ₃-OH)₂( ₃-Br)₂( ₂-Br)₈(OEt₂)₈] (II), are reported. Both compounds were isolated from the same system. The aluminum atom in (I) resides in an almost idealized trigonal planar environment. The dihedral angles of the pentamethylphenyl rings relative to the AlC₃plane in (I) are 67.2, 62.4, and 61.2°. The neutral magnesium cluster, (II), is interesting in that contains six magnesium atoms each of which resides in octahedral environments.     

Synthesis of Palladium Clusters with the P--N--P Assembling Ligands (Ph2P)2CH2 (dppm) and (Ph2P)2NH (dppa). Crystal Structure of [Pd4(μ-Cl)2(μ-dppm)2(μ-dppa)2](PF6)2

Tetrapalladium clusters containing dppa or dppa and dppm bridging ligands were prepared by condensation of dinuclear units. Reaction of [Pd₂Cl₂(-dppa)₂] with [Cu(PPh₃)]PF₆ (generated in situ in THF) yielded [Pd₄(-Cl)₂(-dppa)₄] (PF₆)₂ (4) in a virtually quantitative yield but [Pd₄(-Cl)₂(-dppm)₂(-dppa)₂] (PF₆)₂ (6) was best prepared in CH₂Cl₂ from [Pd₂Cl₂(-dppm)₂] and [Pd₂(MeCN)₂(-dppa)₂](PF₆)₂ (2). The structure of 6·2(CH₃)₂CO·2H₂O was determined by X-ray diffraction. It consists of a planar, centrosymmetric 10-membered ring structure. The four bridging diphosphine ligands are of two types: two dppa ligands support the Pd Pd bonds [2.6055(4) Å], whereas the two dppm ligands bridge between two palladium atoms separated by 3.722(4) Å, which are also bridged by a chloride ligand.     

Synthesis and characterisation of novel selenium-containing clusters; crystal structures of [Ru4(μ4-Se)2(CO)8(μ-CO)3] and [Ru3(μ3-Se)2(CO)7(Ph2P(CH2)3PPh2)]

The compound [Ru₄(μ-Se)₂(CO)₈(μ3-CO)₃] (1), has been obtained in good yield by vacuum pyrolysis of [RU₃(CO)₁₂] with [Ph₂Se₂] at 185°C. Reaction of 1 with 1,3-bis(diphenylphosphino)propane at room temperature affords the novel cluster [RU₃(μ₃-Se)₂(CO)₇(Ph₂P(CH₂)₃PPh₂)] (2). The structures of 1 and 2 have been determined by an X-ray diffraction study.     

Formation of the unusual cluster Cu4(μ4-OH)(μ-(CF3)2pz)4(μ-OOCPh)2(μ-OH)2(OH2)(Et3NH)[O(CH2Ph)2]2 in the thermolysis of a copper μ-aqua complex with bridging pyrazolate and acetate ligands in dibenzyl ether in the presence of atmospheric oxygen

A room-temperature reaction of cupric acetate dihydrate with 3,5-bis(trifluoromethyl)pyrazole ((CF₃)₂pzH) in chloroform in the presence of triethylamine gave a complex of the formula [Cu₂(??-(CF₃)₂pz)₂(??-OH₂)(OC(Me)OHNEt₃)(OH₂)(HCCl₃)(OOCMe)(??-OOCMe)]₂ (2). Heating of this complex at 180°C in dibenzyl ether (DBE) in air yielded the tetranuclear pyrazolate-benzoate cluster Cu₄(??₄-OH)(??-(CF₃)₂pz)₄(??-OOCPh)₂(??-OH)₂(OH₂)(Et₃NH)[O(CH₂Ph)₂]₂. It was suggested that such complexes can be intermediates in the liquid-phase oxidation of DBE with atmospheric oxygen in the presence of copper complexes containing pyrazolate bridges.     

Synthesis and crystal structure of platinum(II) acetamidates [Pt(2,2′-bipy)(NHCOCH3)2] and [enPt(μ-NHCOCH3)(μ-OH)Pten](NO3)2

The diamines PtbipyCl₂, and PtenCl₂ and their aqua and hydroxy derivatives react with acetonitrile to give the Pt(II) acetamidates [Pt(2,2′-bipy)(NHCOCH₃)₂] · 4.125 H₂O (I) and [enPt(μ-NHCOCH₃(μ-OH)Pten](NO₃)₂ · H₂O (II), which are characterized by X-ray diffraction. The crystals of I are triclinic, a = 7.137(10) Å, b = 12.655(3) Å, c = 21.914(6) Å, α = 81.82(2)°, β = 82.12(2)°, γ = 77.72(2)°, V = 1908.6(7) ų, space group P $\overline 1 $ , Z = 4, R = 0.033 for 3700 reflections. Complex I is a mononuclear acetamidate with terminal (NHCOCH₃)^? ligands. The crystals of II are monoclinic, a = 11.413(2) Å, b = 10.981(2) Å, c = 14.385(3) Å, β = 105.90(3)°, V = 1733.8(6) ų, space group P2₁/n, R = 0.028 for 2797 reflections. Complex II is a dimer with bridging (NHCOCH₃)^? and (OH)^? groups. The Pt-Pt distance is 3.1667(7) Å.     

Synthesis and structures of complexes Os3(μ-H)2(CO)7(μ-RC5H3N){μ3-Ph2PCH2P(C6H4)Ph} (R = H, Me) with ortho-metalated pyridine ligands. The revised structure of the triosmium cluster ”Os3(μ-H)2(CO)7(μ-C6H4){μ3-Ph2PCH2P(C6H4)Ph}”

The structure of the previously synthesized triosmium cluster was revised. The structure Os₃(μ-H)₂(CO)₇(μ-C₆H₄){μ₃-Ph₂PCH₂P(C₆H₄)Ph} suggested earlier was not confirmed. The cluster has the composition Os₃(μ-H)₂(CO)₇(μ-C₅H₄N){μ₃-Ph₂PCH₂P(C₆H₄)Ph} and contains the ortho-metalated pyridine ligand. The X-ray diffraction study of the complex Os₃(μ-H)₂(CO)₇(μ-MeC₅H₃N){μ₃-Ph₂PCH₂P(C₆H₄)Ph} containing the ortho-metalated 4-methylpyridine ligand made it possible to distinguish between the C and N atoms of the pyridine ligands in the resulting triosmium clusters.     

Reactivity of ruthenium carbonyl derivatives of lutecium. Molecular structure of (THF)[1, 3-(Me3Si)2C5H3]2Lu(μ-OH)2

The reactivity of the ruthenium carbonyl derivatives of lutecium (THF)Cp'₂LuRu(CO)₂Cp [Cp'=Cp (1) and 1, 3-(Me₃Si)₂C₅H₃ (2)] has been studied. It has been shown that the reactions of complex 1 withi.-Pr₂CO and of2 with HCl, H₂O, and HgCl₂ are accompanied by cleavage of the Lu-Ru bond. The reaction of2 with H₂O gives [1, 3-(Me₃Si)₂C₅H₃]₂Lu (-OH)₂ (3), which has been characterized by X-ray diffraction analysis (MoK radiation,R=0.0280, 2750 reflections). The crystals are monoclinic,a = 15.638(6) Å,b=15.787(2) Å,c = 12.188(1) Å, =99.06°,Z= 2, space group P2₁/n. Centrosymmetric dimer3 has two -OH ligands, and the Lu-O and Lu...Lu interatomic distances are 2.264(4) Å (mean) and 3.579(1) Å, respectively. The structure behavior of3 in a THF solution has been discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 574–577, March, 1993.     

Synthesis and structure of a novel bis-μ-oxo rhenium(VI) dimer: Re2O2(μ-O)2(CH2CMe2Ph)4

The complex Re(O)Cl₃(PPh₃)₂ reacts with dialkyl zinc reagents in CH₂Cl₂ to give the novel bis-μ-oxo rhenium(VI) dimer [Re(O)(μ-O)R₂]₂. The molecular structure has been determined by single-crystal X-ray diffraction methods.