FeCo2(CO)7(μ3-S)(O[P(SCH2)2]2)的合成与晶体结构

许多化学工作者对单齿膦配体（ＰＰｈ３,ＰＢｕｎ３,ＰＥｔ２Ｐｈ,Ｐ（ＯＥｔ）３,Ｐ（ＯＣ６Ｈ５）３）与母体簇合物ＦｅＣｏ２（ＣＯ）９（μ３－Ｓ）的取代反应进行过详细研究［１－３］,但对双齿膦配体与母体簇合物的取代反应研究报导较少．Ａｉｍｅ［４］合成了含双齿膦配体的簇合物ＦｅＣｏ２（ＣＯ）７（μ３－Ｓ）（Ｐｈ２ＰＣＨ２ＰＰｈ２）,并用１３ＣＮＭＲ和ＩＲ光谱方法对其结构进行了表征．到目前为止,含双齿膦配体的该类簇合物的晶体与分子结构还未见报导．ＲｏｓａｎｎａＲｏｓｓｅｔｔｉ［２］通过研究母体簇合物与…     

Palladium(I) carbonyl carboxylate clusters cyclo-[Pd2(μ-CO)2(μ-OCOR)2]n (n = 2 or 3): Structure and reactivity

The interaction of palladium(+1) cluster Pd₄(μ-CO)₄(μ-OAc)₄ with saturated and unsaturated carboxylic acids was studied. It was found, that the substitution of acetates groups on others carboxylates leads to the clusters with different nuclearity. Palladium(+1) carbonyl carboxylate complexes of composition [Pd(μ-CO)(μ-OCOR)]_n, where R = CF₃, CCl₃, CH₂Cl, MeCH = CMe, Me, Prⁱ, Bu, Buⁱ, Bu^tert, n-C₅H₁₁ and n = 4 or 6 were synthesized. According to X-ray data all clusters possess cyclic planar metal cores with alternate pairs of μ-carbonyl and μ-carboxylate ligands. The presence of bulky alkyl fragments in the carboxylate ligand increases the nuclearity of the cluster compared to that of the starting palladium(+1) carbonyl acetate of composition Pd₄(μ-CO)₄(μ-OAc)₄ due, apparently, to steric hindrance.     

Synthesis and structure of mixed-metal thiolate complex Cp′Cr(CO)2(μ-SBu)Pt(PPh3)2: Side-on-coordination of Cr–S double bond with platinum

The reaction of [Cp′Cr(CO)₂(μ-SBu)]₂ (1) (Cp′ = MeC₅H₄) with (PPh₃)₂Pt(PhCCPh) gives Cp′Cr(CO)₂(μ-SBu)Pt(PPh₃)₂ (2) which could be regarded as a product of the substitution of acetylene ligand at platinum by a monomeric chromium–thiolate fragment. According to the X-ray diffraction analysis 2 contains single Cr–Pt (2.7538(15)) and Pt–S (2.294(2) Å) bonds while Cr–S bond (2.274(3) Å) is shortened in comparison with ordinary Cr–S bonds (2.4107(4)–2.4311(4) Å) in 1. The bonding between Cr–S fragment and platinum atom is similar to the olefine coordination in their platinum complexes.     

Mixed-metal single-molecule magnets: Syntheses, structure, and magnetic properties of [Mn8Fe4O12(O2CR)16(H2O)4] (R = CH2Cl, CH2Br, CHCl2)

Three mixed-metal single-molecule magnets containing [Mn₈Fe₄O₁₂]¹⁶⁺ cores are synthesized and characterized. The reaction of FeCl₂·4H₂O with KMnO₄ and RCOOH (R = CH₂Cl, CH₂Br) in H₂O gives [Mn₈Fe₄O₁₂(O₂CR)₁₆(H₂O)₄] (R = CH₂Cl (1), CH₂Br (2)) in yields of 43% and 40%, respectively. Treatment of complex 1 with an excess of CHCl₂COOH in CH₂Cl₂ gives [Mn₈Fe₄O₁₂(O₂CCHCl₂)₁₆(H₂O)₄]·CH₂Cl₂·10H₂O (3·CH₂Cl₂·10H₂O) in a yield of 83%. The X-ray structure analysis reveals that all three complexes consist of a trapped-valence dodecanuclear core comprising 4Mn^III, 4Fe^III, and 4Mn^IV ions. DC magnetic susceptibility and magnetization measurements indicate that all three complexes exhibit intramolecular antiferromagnetic interaction, resulting in an S = 4 ground state. In addition, frequency-dependent out-of-phase AC magnetic susceptibility signals at low temperature for complexes 1, 2, and 3 are indicative of their single-molecule magnetism behavior.     

Synthesis and X-ray crystal structures of [Ru4H4(CO) 11(PPh3)] and [Ru4−x IrxH2−x(CO) 12(PPh3) ] (x = 0 or 1)

Three tetranuclear clusters [Ru₄H₄(CO)₁₁(PPh₃)] (1), [Ru₄H₂(CO)₁₂(PPh₃)] (2) and [Ru₃IrH(CO)₁₂(PPh₃)] (3) were formed in the reaction of [Ir(CO)Cl(PPh₃)₂] and Na[Ru₃H(CO)₁₁] in tetrahydrofuran. Complexes 1–3 were characterized by IR and ¹H and ³¹P NMR, and the structure of the clusters was confirmed by single crystal X-ray analysis. In 2 and 3 one of the carbonyls bridges between two ruthenium atoms; otherwise the compounds contain only terminal carbonyls.     

New alkali-metal-molybdenum(VI)-selenium(IV) oxides: syntheses, structures, and characterization of A2SeMoO6 (A=Na, K, or Rb)

Three new quaternary selenites, A₂SeMoO₆ (A=Na⁺, K⁺, or Rb⁺), were synthesized through the solid-state reaction of A₂MoO₄ with SeO₂ at 400°C. Although the reported materials are ‘stoichiometrically equivalent’, the compounds exhibit strikingly different crystal structures. Whereas Na₂SeMoO₆ has a three-dimensional crystal structure, K₂SeMoO₆ and Rb₂SeMoO₆ are molecular and uni-dimensional, respectively. However, all of the new materials have structures containing Mo⁶⁺ octahedra linked to Se⁴⁺ trigonal pyramids. Although the Mo⁶⁺ and Se⁴⁺ cations are in local asymmetric environments in all three materials, only Na₂SeMoO₆ is non-centrosymmetric. Single crystal X-ray data: Na₂SeMoO₆, cubic, space group, P2₁3 (no. 198), a=8.375(5) Å, Z=4, R(F)=0.0143; K₂SeMoO₆, monoclinic, space group, P2₁/c (no. 14), a=6.118(8) Å, b=15.395(2) Å, c=7.580(9) Å, β=112.39(4)°, Z=4, R(F)=0.0281; Rb₂SeMoO₆, orthorhombic, space group, Pnma (no. 62), a=7.805(9) Å, b=6.188(7) Å, c=14.405(4) Å, Z=4, R(F)=0.0443.     

Synthesis and characterization of Na11[CuO4][SO4]3

Na₁₁[CuO₄][SO₄]₃ was obtained from a redox reaction of CuO with Na₂O₂ in the presence of Na₂O and Na₂SO₄ in sealed Ag containers under Ar atmosphere at 600°C. The crystal structure has been determined from X-ray single crystal data at 293 and 170 K (Pnma, Z=4). The lattice parameters have been refined from X-ray powder data at 293 K as well: a=1597.06(6) pm, b=703.26(3) pm, c=1481.95(6) pm. The structure contains isolated distorted square-planar [CuO₄]⁵⁻ anions and non-coordinating sulfate groups. Furthermore, we report calculations of the Madelung Part of the Lattice Energy (MAPLE) and some of the physical properties of Na₁₁[CuO₄][SO₄]₃.     

Synthesis and characterization of monomeric siloxo palladium(II) complexes: crystal structure of [Pd(tmeda)(C6F5)(OSiPh3)]

Mononuclear palladium-hydroxo complexes of the type [Pd(N-N)(C₆F₅)(OH)] [(N-N)=2,2^′-bipyridine (bipy), 4,4^′-dimethyl-2,2^′-bipyridine (Me₂bipy), or N,N,N^′,N^′-tetramethylethylenediamine (tmeda)] react with silanols HOSiR₃ in toluene giving the corresponding siloxo complexes [Pd(N-N)(C₆F₅)(OSiR₃)]. The X-ray crystal structure of [Pd(tmeda)(C₆F₅)(OSiPh₃)] has been determined. In one of the two molecules in the asymmetric unit there is an intramolecular interaction by phenyl-pentafluorophenyl π-stacking.     

Reaction of [CpRu(CH3CN)3]PF6 with bidentate ligands: structural characterization of [{CpRu(CH3CN)2}2(μ-η-dppe)](PF6)2 [dppe=1,2-bis(diphenylphosphino)ethane]

The reaction of [CpRu(CH₃CN)₃]PF₆ with the bidentate ligands L-L=1,2-bis(diphenylphosphino)ethane, dppe, and (1-diphenylarsino-2-diphenylphosphino)ethane, dpadppe, affords mononuclear or dinuclear complexes of formula [CpRu(η²-L-L)(CH₃CN)]PF₆, [{CpRu(CH₃CN)₂}₂(μ-η^1:1-L-L)](PF₆)₂ and [{CpRu(CH₃CN)}₂(μ-η^1:1-L-L)₂](PF₆)₂ (L-L=dppe, dpadppe). All of the compounds are characterized by microanalysis and NMR [¹H and ³¹P{¹H}] spectroscopy. The crystal structure of [{CpRu(CH₃CN)₂}₂(μ-η^1:1-dppe)](PF₆)₂ has been determined by X-ray diffraction analysis. The complex exhibits a dppe ligand bridging two CpRu(CH₃CN)₂ fragments.     

Synthesis, structural characterization and ex vivo biological properties of a new complex [Cu(propranolol)2]·2H2O, a potential beta-blocker

The synthesis and spectroscopic characterization (UV–Vis, IR, EPR) of a new copper complex with a beta-blocker propranolol (1-(isopropylamino)-3-(1-naphthyloxy)-2-propanol) are presented. Besides, the X-ray crystal structure of [Cu(propranolol)₂]·2H₂O is determined, showing two different copper ions, one coordinated through two S propranolol isomers and the other through two R isomers. The effect on the heart contraction force and on the heart rate plus the block of response to adrenaline of the complex and the free ligand, were studied. The effect of [Cu(propranolol)₂]·2H₂O on contractility was very similar to that of the free propranolol while the reduction on the heart rate is approximately 30% of the reduction obtained with the free ligand. This is an encouraging result since the search of new beta-blocker drugs that have lesser effect on heart rate is one of the important topics in cardiac pharmacology. The block of the response to adrenaline is at least similar for both ligand and complex.     

Dodecanuclear rhenium cluster complexes with an interstitial carbon atom: Synthesis, structures and properties of two new compounds K6[Re12CS17(OH)6]·4H2O and Na12Re12CS17(SO3)6·48.5H2O

The dodecanuclear rhenium anionic complex with terminal hydroxo ligands [Re₁₂CS₁₇(OH)₆]⁶⁻ was obtained by the reaction of K₆[Re₁₂CS₁₇(CN)₆]·20H₂O with molten KOH at 300 °C. The cluster complex was crystallized as a potassium salt from aqueous solution. The reaction between K₆[Re₁₂CS₁₇(OH)₆]·4H₂O and Na₂S₂O₄ in water under reflux results in the formation of the complex Na₁₂[Re₁₂CS₁₇(SO₃)₆]·48.5H₂O. Both new compounds were characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The electronic structure of [Re₁₂CS₁₇(OH)₆]⁶⁻ was also elucidated by DFT calculations.     

Hydrothermal syntheses and crystal structures of bimetallic cluster complexes [{Cd(phen)2}2V4O12]·5H2O and [Ni(phen)3]2[V4O12]·17.5H2O

The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen₂)₂V₄O₁₂]·5H₂O (1) and [Ni(phen)₃]₂[V₄O₁₂]·17.5H₂O (2). Crystal data: C₄₈H₅₂Cd₂N₈O₂₂V₄ (1), triclinic. a=10.3366(10), b=11.320(3), c=13.268(3) Å, =103.888(17)°, β=92.256(15)°, γ=107.444(14)°, Z=1; C₇₂H₁₃₁N₁₂Ni₂O_29.5V₄ (2), triclinic. a=12.305(3), b=13.172(6), c=15.133(4), =79.05(3)°, β=76.09(2)°, γ=74.66(3)°, Z=1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59° <θ<26.02° and 2.01°<θ<25.01° using the ω-scan technique, respectively. The structure of 1 consists of a [V₄O₁₂]⁴⁻ cluster covalently attached to two {Cd(phen)₂}²⁺ fragments, in which the [V₄O₁₂]⁴⁻ cluster adopts a chair-like configuration. In the structure of 2, the [V₄O₁₂]⁴⁻ cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the [V₄O₁₂]⁴⁻ unit and crystallization water molecules.     

Reactions of hydrosulfido- and hydroselenido-bridged dinuclear Ir, Rh, and Ru complexes with SbCl3 and BiCl3 affording mixed-metal sulfido and selenido clusters containing both noble metals and Group 15 metals

A new versatile method to synthesize a series of noble metal-Group 15 metal chalcogenido clusters has been found. Thus, treatment of the hydrosulfido- or hydroselenido-bridged dinuclear complexes [Cp*MCl(μ-EH)₂MCp*Cl] (M=Ir, Rh; E=S, Se; Cp*=η⁵-C₅Me₅), [Cp°RuCl(μ-SH)₂RuCp°Cl] (Cp°=η⁵-C₅EtMe₄), and [Ru(L)Cl(μ-SH)₂Ru(L)Cl] (L=η⁶-C₆Me₅H) with M^′Cl₃ (M^′=Sb, Bi) in THF at room temperature afforded smoothly the clusters [Cp*MCl(μ-EM^′Cl₂)₂MCp*Cl], [Cp°RuCl(μ-SM^′Cl₂)₂RuCp°Cl], and [Ru(L)Cl(μ-SM^′Cl₂)₂Ru(L)Cl] through dehydrochlorination. The X-ray analyses of eleven new clusters clarified the details of their structures consisting of the cubane-type M₂M^′₂E₂Cl₂ cores resulting from the presence of weak MCl?M^′ bonding interactions in addition to the normal M-E, M-Cl, and M^′-E bonds.     

Synthesis and structures of heterobimetallic Ir2M (M=Pd, Pt) sulfido clusters and their catalytic activity for regioselective addition of alcohols to internal 1-aryl-1-alkynes

The heterobimetallic trinuclear sulfido clusters [(Cp*Ir)₂(μ₃-S)₂MCl₂] (M=Pd (3), Pt (4); Cp*=η⁵-C₅Me₅) were synthesized from the dinuclear hydrogensulfido complex [Cp*IrCl(μ-SH)₂IrCp*Cl] (2) and [MCl₂(COD)] (COD=cycloocta-1,5-diene), while the reaction of 2 with [Pd(PPh₃)₄] afforded the cationic trinuclear cluster [(Cp*Ir)₂(μ₃-S)₂PdCl(PPh₃)]Cl (5). Clusters 3 and 4 reacted with PPh₃ to give a series of mono and dicationic clusters including 5, while the dicationic clusters [(Cp*Ir)₂(μ₃-S)₂M(dppe)][BPh₄]₂ (M=Pd (9), Pt (10); DPPE=Ph₂PCH₂CH₂PPh₂) were obtained by the reaction with dppe followed by anion metathesis. The molecular structures of 5·CH₂Cl₂, 9·CH₃COCH₃, and 10·CH₃COCH₃ were determined by X-ray crystallography. Clusters 3 and 4 were found to catalyze the addition of alcohols to alkynes to give the corresponding acetals. Internal 1-aryl-1-alkynes were transformed by cluster 3 into the corresponding 2,2-dialkoxy-1-arylalkanes with high regioselectivity up to 99:1, while cluster 4 was a much less regioselective catalyst.     

Synthesis,crystal structure and magnetic properties of the helical oxalate-bridged copper(II) chain {[(CH3)4N]2[Cu(C2O4)2] · H2O}n

The preparation, crystal structure and magnetic properties of a new oxalate-containing copper(II) chain of formula {[(CH₃)₄N]₂[Cu(C₂O₄)₂] · H₂O}_n (1) [(CH₃)₄N⁺ = tetramethylammonium cation] are reported. The structure of 1 consists of anionic oxalate-bridged copper(II) chains, tetramethylammoniun cations and crystallization water molecules. Each copper(II) ion in 1 is surrounded by three oxalate ligands, one being bidentate and the other two exhibiting bis-bidenate coordination modes. Although all the tris-chelated copper(II) units from a given chain exhibit the same helicity, adjacent chains have opposite helicities and then an achiral structure results. Variable-temperature magnetic susceptibility measurements of 1 show the occurrence of a weak ferromagnetic interaction through the oxalate bridge [J = +1.14(1) cm⁻¹, the Hamiltonian being defined as H = –J ∑_nmS_i · S_j]. This value is analyzed and discussed in the light of available magneto-structural data for oxalate-bridged copper(II) complexes with the same out-of-plane exchange pathway.     

One- or two-dimensional organometallic arrays containing PdIr2(μ3-S)2 mixed-metal sulfido cluster units connected via the nicotinamide or isonicotinamide ligands on their Pd sites through hydrogen-bonding interactions

Mixed-metal sulfido cluster [(PdCl₂)(Cp*Ir)₂(μ₃-S)₂] (Cp*=η⁵-C₅Me₅) dissolved in CH₂Cl₂ reacted with two equivalent of L (L=nicotinamide, isonicotinamide, or N-methylnicotinamide) in the presence of AgBF₄ to give the cationic clusters [(PdL₂)(Cp*Ir)₂(μ₃-S)₂][BF₄]₂. The single-crystal X-ray diffraction studies of these products have disclosed that in the solid state the PdIr₂S₂ cores are self-assembled to form one-dimensional chains through the intermolecular hydrogen-bonding between the amide groups for L=nicotinamide or two-dimensional sheets via the hydrogen-bonding between the amide groups and the BF₄ anions for L=isonicotinamide, whereas no organization of the cluster cores is observed for L=N-methylnicotinamide.     

Synthesis and structures of new niobium cluster compounds with pyridinium cations: (PyrH)2[Nb6Cl18]·EtOH (Pyr: pyridine, Et: ethyl) and the cubic modification of (PyrH)2[Nb6Cl18]

Slow crystallization of (PyrH)₂[Nb₆Cl₁₈] from hot ethanol solution affords triclinic (PyrH)₂[Nb₆Cl₁₈]·EtOH. Treatment of [Nb₆Cl₁₄(H₂O)₄]·4H₂O with pyridine in a methanol solution gives the second title compound, the cubic modification of (PyrH)₂[Nb₆Cl₁₈]. Both structures were determined by single crystal X-ray diffraction, (PyrH)₂[Nb₆Cl₁₈]·EtOH: P1¯, a=9.3475(3), b=9.3957(3), c=10.8600(3) Å, α=82.582(1)°, β=78.608(1)°, and γ=78.085(1)°, Z=1, R₁(F)/wR₂(F²)=0.0254/0.0573, cub.-(PyrH)₂[Nb₆Cl₁₈]: Fd3¯m, a=19.935(2) Å, Z=8, R₁(F)/wR₂(F²)=0.0557/0.1796. The cluster compounds contain isolated, molecular [Nb₆Clⁱ₁₂Cl^a₆]²⁻ cluster anions with an octahedron of metal atoms edge bridged by chlorido ligands with additional ones on all the six exo positions. These cluster anions are separated by the pyridinium cations and ethanol solvent molecules, respectively. For the cubic modification of (PyrH)₂[Nb₆Cl₁₈], a structural comparison is given to the known rhombohedral modification using the group-subgroup relations as expressed by a Bärnighausen tree.     

Syntheses, crystal structures and spectroscopic properties of Ag2Nb[P2S6][S2] and KAg2[PS4]

Ag₂Nb[P₂S₆][S₂] (1) was obtained from the direct solid state reaction of Ag, Nb, P₂S₅ and S at 500 °C. KAg₂[PS₄] (2) was prepared from the reaction of K₂S₃, Ag, Nd, P₂S₅ and extra S powder at 700 °C. Compound 1 crystallizes in the orthorhombic space group Pnma with a=12.2188(11), b=26.3725(16), c=6.7517(4) Å, V=2175.7(3) Å³, Z=8. Compound 2 crystallizes in the non-centrosymmetric tetragonal space group with lattice parameters a=6.6471(7), c=8.1693(11) Å, V=360.95(7) Å³, Z=2. The structure of Ag₂Nb[P₂S₆][S₂] (1) consists of [Nb₂S₁₂], [P₂S₆] and new found puckered [Ag₂S₄] chains which are along [001] direction. The Nb atoms are located at the center of distorted bicapped trigonal prisms. Two prisms share square face of two [S₂²⁻] to form one [Nb₂S₁₂] unit, in which Nb-Nb bond is formed. The [Nb₂S₁₂] units share all S²⁻ corners with ethane-like [P₂S₆] units to form 14-membered rings. The novel puckered [Ag₂S₄] chains are composed of distorted [AgS₄] tetrahedra and [AgS₃] triangles that share corners with each other. These chains are connected with [P₂S₆] units and [Nb₂S₁₂] units to form three-dimensional frame work. The structural skeleton of 2 is built up from [AgS₄] and [PS₄] tetrahedra linked by corner-sharing. The three-dimensional anionic framework contains orthogonal, intersecting tunnels directed along [100] and [010]. This compound possesses a compressed chalcopyrite-like structure. The structure is compressed along [001] and results from eight coordination sphere for K⁺. Both compounds are characterized with UV/vis diffuse reflectance spectroscopy and compound 1 with IR and Raman spectra.     

Solvothermal synthesis and characterisation of new one-dimensional indium and gallium sulphides: [C10N4H26]0.5[InS2] and [C10N4H26]0.5[GaS2]

Two new main group metal sulphides, [C₁₀N₄H₂₆]_0.5[InS₂] (1) and [C₁₀N₄H₂₆]_0.5[GaS₂] (2) have been prepared solvothermally in the presence of 1,4-bis(3-aminopropyl)piperazine and their crystal structures determined by single-crystal X-ray diffraction. Both compounds are isostructural and crystallise in the monoclinic space group P2₁/n (Z=4), with a=6.5628(5), b=11.2008(9), c=12.6611(9) Å and β=94.410(4)° (wR=0.035) for compound (1) and a=6.1094(5), b=11.2469(9), c=12.7064(10) Å and β=94.313(4)° (wR=0.021) for compound (2). The structure of [C₁₀N₄H₂₆]_0.5[MS₂] (M=In,Ga) consists of one-dimensional [MS₂]⁻ chains which run parallel to the crystallographic a axis and are separated by diprotonated amine molecules. These materials represent the first example of solvothermally prepared one-dimensional gallium and indium sulphides.     

Synthesis and characterisation of the platinum complexes [PtCl(CClPAr)(PPh3)2] and [PtCl(CClPAr′)(PPh3)2] as potential intermediates in the preparation of phosphaalkynes

Oxidative addition reactions of Cl₂CPR (R = 2,4,6-tris(trifluoromethyl)phenyl (Ar) or 2,6-bis(trifluoromethyl)phenyl (Ar′) with Pt(PPh₃)₄ yield the cis and trans (at platinum) complexes [PtCl(ClCPAr)(PPh₃)₂] and [PtCl(ClCPAr′)(PPh₃)₂]. All starting materials and intermediates have been characterised by NMR spectroscopy. The crystal and molecular structures of the trans-platinum complexes have been determined by single-crystal X-ray diffraction at low temperature.