A Functionalized Ag2S Molecular Architecture: Facile Assembly of the Atomically Precise Ferrocene‐Decorated Nanocluster [Ag74S19(dppp)6(fc(C{O}OCH2CH2S)2)18]

A ferrocene‐based dithiol 1,1′‐[fc(C{O}OCH₂CH₂SH)₂] has been prepared and treated with a Ag^I salt to form the stable dithiolate compound [fc(C{O}OCH₂CH₂SAg)₂]_n (fc=[Fe(η⁵‐C₅H₄)₂]). This is used as a reagent for the preparation of the nanocluster [Ag₇₄S₁₉(dppp)₆(fc(C{O}OCH₂CH₂S)₂)₁₈] which was obtained in good yield (dppp=1,3‐bis(diphenylphosphino)propane).     

簇合物[(WS4)2Ag4(dppm)3]·Py·DMF的低加热固相合成与晶体结构

通过低加热固相合成法制备了六核簇合物[(WS4)2Ag4(dppm)3]·Py·DMF,用单晶X-射线衍射法测得该晶体属单斜晶系,空间群P21/c,晶胞参数a＝2.2990(4),b＝1.4094(2),c＝2.8083(5)nm,β＝107.472(2)°,V＝8.680(2)nm3,Z＝4,DC＝1.807 g/cm3,μ＝38.72 cm-1,F(000)＝4608,R＝0.0482,wR＝0.0987.[(WS4)2Ag4(dppm)3]的分子结构含有二个WS4Ag2簇单元和三个dppm配体,其中一个dppm配体连接同一WS4Ag2簇单元内的Ag(1)和Ag(2)原子,而另二个dppm配体则分别和不同WS4Ag2簇单元内的二个Ag原子桥联.     

Niobium Alcoholate Clusters with an Octahedral Arrangement of Metal Atoms: [K(CH3OH)4]2 [Nb6(OCH3)18] and [Na([18]crown‐6)(C2H5OH)2]2 [Nb6(OC2H5)12(NCS)6]

Complete exchange : [M₆X₁₂] type cluster compounds with an octahedral M₆ metal atom arrangement, which is completely surrounded by alcoholato ligands, were unknown until now. The first representatives are prepared containing a [Nb₆(OR)₁₂]⁴⁺ unit (R=CH₃ or C₂H₅). They are accessible at elevated temperatures from strongly basic alcoholate solutions of [Nb₆Cl₁₂]²⁺‐containing precursors. C gray, H white, K turquoise, Nb blue, O red.

     

Syntheses and structures of sterically congested linear and branched cobalta[n]triangulanes

Treatment of {eta(5):eta(1)[2-(di-tert-butylphosphanyl-P)ethyl]cyclopentadienyl}cobalt(I) chloride (5) with methylenecyclopropane (3) or bicyclopropylidene (4), as well as with their spirocyclopropanated analogues methylenespiropentane (7), cyclopropylidenespiropentane (10), or 7,7'-bi(dispiro[2.0.2.1]heptylidene) (15) in the presence of sodium amalgam at -50 degrees C, furnished the stable cobalt complexes 6, 9, 8, 11, and 16, respectively, in 72, 83, 84, 86, and 54 % isolated yield, respectively. The complexes 14 and 16 were also obtained by ligand exchange of the ethene complex {eta(5):eta(1)[2-(di-tert-butylphosphanyl-P)ethyl]cyclopentadienyl}(eta(2)-ethene)cobalt(I) (12) with 13 and 15 in 79 and 52 % yield, respectively. The X-ray crystal-structure analyses of complexes 9, 14, and 16, as well as the NMR-spectroscopic data of all complexes, reveal that they can be regarded as linear and branched cobalta[n]triangulanes. The thermal stability of complexes 6, 8, and 9 up to 109, 145, and 160 degrees C was determined by differential thermal analysis-thermogravimetry (DTA-TG) analysis.     

Synthesis and characterisation of nu3-octahedral [Ni36Pd8(CO)48]6- and [Ni35Pt9(CO)48]6- clusters displaying unexpected surface segregation of Pt atoms and molecular and/or crystal substitutional Ni/Pd and Ni/Pt disorder

The synthesis and structure, as well as the chemical and electrochemical characterisation of two new nu(3)-octahedral bimetallic clusters with the general [Ni(44-x)M(x)(CO)(48)](6-) (M = Pd, x = 8; M = Pt, x = 9) formula is reported. The [Ni(35)Pt(9)(CO)(48)](6-) cluster was obtained in reasonable yields (56 % based on Pt) by reaction of [Ni(6)(CO)(12)](2-) with 1.1 equivalents of Pt(II) complexes, in ethyl acetate or THF as the solvent. The [Ni(36)Pd(8)(CO)(48)](6-) cluster was obtained from the related reaction with Pd(II) salts in THF, and was isolated only in low yields (5-10 % based on Pd), mainly because of insufficient differential solubility of its salts. The unit cell of the [NBu(4)](6)[Ni(35)Pt(9)(CO)(48)] salt contains a substitutionally Ni-Pt disordered [Ni(24)(Ni(14-x)Pt(x))Pt(6)(CO)(48)](6-) (x = 3) hexaanion. A combination of crystal and molecular disorder is necessary to explain the disordering observed for the Ni/Pt sites. The unit cell of the corresponding [Ni(36)Pd(8)(CO)(48)](6-) salt contains two independent [Ni(30)(Ni(8-x)Pd(x))Pd(6)(CO)(48)](6-) (x = 2) hexaanions. The two display similar substitutional Ni-Pd disorder, which probably arises only from crystal disorder. The structure of [Ni(36)Pd(8)(CO)(48)](6-) establishes the first similarity between the chemistry of Ni-Pd and Ni-Pt carbonyl clusters. A comparison of the chemical and electrochemical properties of [Ni(35)Pt(9)(CO)(48)](6-) with those of the related [Ni(38)Pt(6)(CO)(48)](6-) cluster shows that surface colouring of the latter with Pt atoms decreases redox as well as protonation propensity of the cluster. In contrast, substitution of all internal Pt and two surface Ni with Pd atoms preserves the protonation behaviour and is only detrimental with respect to its redox aptitude. A qualitative rationalisation of the different surface-site selectivity of Pt and Pd, based on distinctive interplays of M--M and M--CO bond energies, is suggested.     

Structure of Ag clusters Grown on Fs-Defect Sites of an MgO(1 0 0) surface

The structure of AgN clusters (N=1-4, 6, 8, 10), both in the gas phase and grown on the MgO(1 0 0) surface containing Fs-defects, has been investigated by a density functional basin-hopping (DF-BH) approach. In analogy with what observed in the case of gold clusters, it is found that the presence of the defect implies a double frustration and a cylindrical invariance of the metal-surface interaction, causing small Ag clusters growing around the Fs defect to be highly fluxional. Nevertheless, two different structural crossovers are found to be induced by the metal-defect interaction for the adsorbed clusters such that: 1) planar structures prevail for Nor=7), prevail for N=6 and N=8; 3) distorted face-centered cubic (fcc) structures grown pseudomorphically on the defected surface prevail for N=10. The transition from fivefold to fcc motifs is rationalized in terms of the double-frustration effect, which increases the bond strain of the noncrystalline structures. Detrapping energies from the defect were also calculated; the lowest energy pathway corresponds to the detachment of a dimer.     

Copper(I) alkynyl clusters, [Cu(x+y)(hfac)(x)(C[triple chemical bond]CR)(y)], with Cu(10)-Cu(12) cores

The facile syntheses and the structures of five new Cu(I) alkynyl clusters, [Cu(12)(hfac)(8)(C[triple chemical bond]CnPr)(4)(thf)(6)]xTHF (1), [Cu(12)(hfac)(8)(C[triple chemical bond]CtBu)(4)] (2), [Cu(12)(hfac)(8)(C[triple chemical bond]CSiMe(3))(4)] (3), [Cu(10)(hfac)(6)(C[triple chemical bond]CtBu)(4)(diethyl ether)]/[Cu(10)(hfac)(6)(C[triple chemical bond]CtBu)(3)(C[triple chemical bond]CnPr)(diethyl ether)] (4) and [Cu(10)(hfac)(6)(C[triple chemical bond]CtBu)(4)(diethyl ether)] (5) are reported, in which hfacH=1,1,1,5,5,5-hexafluoropentan-2,4-dione. The first independent molecule found in the crystals of 4 (4 a) proved to be chemically identical to 5. The Cu(10) and Cu(12) cores in these clusters are based on a central "square" Cu(4)C(4) unit. Whilst the connectivities of the Cu(10) or Cu(12) units remain identical the geometries vary considerably and depend on the bulk of the alkynyl group, weak coordination of ether molecules to copper atoms in the core and CuO intramolecular contacts formed between Cu-hfac units on the periphery of the cluster. Similar intermolecular contacts and interlocking of Cu-hfac units are formed in the simple model complex [Cu(2)(hfac)(2)(HC[triple chemical bond]CtBu)] (6). When linear alkynes, C(n)H(2n+1)C[triple chemical bond]CH, are used in the synthesis and non-coordinating solvents are used in the workup, further association of the Cu(4)C(4) cores occurs and clusters with more than eighteen copper atoms are isolated.     

Structure Determination of [Au18(SR)14]

Unravelling the atomic structures of small gold clusters is the key to understanding the origin of metallic bonds and the nucleation of clusters from organometallic precursors. Herein we report the X‐ray crystal structure of a charge‐neutral [Au₁₈(SC₆H₁₁)₁₄] cluster. This structure exhibits an unprecedented bi‐octahedral (or hexagonal close packing) Au₉ kernel protected by staple‐like motifs including one tetramer, one dimer, and three monomers. Until the present, the [Au₁₈(SC₆H₁₁)₁₄] cluster is the smallest crystallographically characterized gold cluster protected by thiolates and provides important insight into the structural evolution with size. Theoretical calculations indicate charge transfer from surface to kernel for the HOMO–LUMO transition.