四面体异核金属羰基簇合物的合成、表征及单晶结构分析

利用金属交换反应, 使金属羰基配合物PhCCo~3(CO)~9和过渡金属配合物NaMo(CO)~3(RCp)在THF中回流反应, 制备出三个新的异核三金属羰基簇合物PhCCo~2Mo(CO)~8(RCp)(R=HCO, CH~3CO, C~2H~5O~2C)。结果表明, 与金属交换剂NaMo(CO)~3Cp相比较, 环戊二烯上吸电子基团C=O的存在减弱了金属交换剂NaMo(CO)~3(RCp)的交换活性。同时发现加热可加速该反应向产物的转化以及进一步证明了该金属交换反应的普遍性。对合成的簇合物进行了元素分析, 红外和氢的核磁谱的结构表征。对簇合物PhCCo~2(CO)~8(C~2H~5O~2CCp)的单晶进行了X射线结构测定, 该晶体属于单斜晶系, 空间群为P2~1/c, 晶胞参数: α=1.1356(2)nm,b=1.4030(2)nm, c=1.6076(3)nm, β=107.19(1)°, Z=4。D~c=1.80g/cm^3,R=0.048, Rw=0.057。     

Decoupling two-dimensional NMR spectroscopy in both dimensions: pure shift NOESY and COSY

An increase in the resolving power in 2D NMR spectra is obtained by collapsing 2D signals with multiplet structure into 2D singlets. This resolution gain is achieved by combining 2D experiments with pure shift techniques and covariance processing (see picture). The method should be of value in both manual and automated structure determination.     

Solid state13C NMR spectra of metal carbonyl clusters

The solid state¹³C NMR spectra of four¹³CO enriched carbonyl clusters having a tri-iron metallic core have been analyzed to provide structural and dynamic information. In Fe₃(CO)₁₂ (1), the high temperature spectra suggest the occurrence of large amplitude motions of the CO groups around their position at the vertexes of the coordination polyhedron in addition to the motion involving the Fe₃-triangle previously detected in the VT-¹³C MAS spectra.¹³C and³¹P NMR data of Fe₃(CO)₁₁PPh₃ (2) indicates the presence of one molecule in the asymmetric unit in apparent disagreement with the previously reported X-ray data. Furthermore, we show that structural information can be obtained from the chemical shift tensor components readily available from the analysis of the spinning sideband manifold.     

Synthesis and characterisation of high-nuclearity osmium-silver mixed-metal clusters

The reaction of the triosmium cluster anion, [Os(3)(micro-H)(CO)(11)][PPN] (PPN = [N(PPh(3))2]+), with [AgPF(6)] in the presence of [Ir(PPh(3))2(CO)Cl] in THF at room temperature affords two new high-nuclearity osmium-silver clusters, [Os(13)Ag(9)(CO)48][PPN] (1) and [Os(9)Ag(9)(micro3-O)2(CO)30][PPN] (2), and an iridium complex, [Ir(PPh(3))2(CO)Cl(O(2))] (3).     

A Quadrupole-Central-Transition 59Co NMR Study of Cobalamins in Solution

We report the first observation of quadrupole-central-transition (QCT) ⁵⁹Co (I=7/2) NMR signals from three cobalamin (Cbl) compounds (CNCbl, MeCbl, and AdoCbl) dissolved in glycerol/water. Measurements were performed at four magnetic fields ranging from 11.7 to 21.1 T. We found that the ⁵⁹Co QCT signals observed for cobalamin compounds in the slow motion regime (ω₀τ_C≫1) are significantly narrower than those observed from their aqueous solutions where the molecular tumbling is near the condition of ω₀τ_C≈1. We demonstrated that an analysis of ⁵⁹Co QCT signals recorded over different temperatures and at multiple magnetic fields allowed determination of both the ⁵⁹Co quadrupole coupling constant and chemical shift anisotropy for each of the three cobalamins. We successfully applied the ⁵⁹Co QCT NMR approach to monitor in situ the transformation of CNCbl to its “base off” form in the presence of KCN. We further discovered that, to obtain the maximum QCT signal intensity with the Hahn-echo sequence, a strong B₁ field should be used for the first 90° pulse, but a weak B₁ field for the second 180° pulse. The reported ⁵⁹Co QCT NMR methodology opens up a new direction for studying structure and function of cobalamin compounds and their roles in biological processes.     

Simulation of 59Co NMR chemical shifts in aqueous solution

59Co chemical shifts were computed at the GIAO-B3LYP level for [Co(CN)6]3-, [Co(H2O)6]3+, [Co(NH3)6]3+, and [Co(CO)4]- in water. The aqueous solutions were modeled by Car-Parrinello molecular dynamics (CPMD) simulations, or by propagation on a hybrid quantum-mechanical/molecular-mechanical Born-Oppenheimer surface (QM/MM-BOMD). Mean absolute deviations from experiment obtained with these methods are on the order of 400 and 600 ppm, respectively, over a total delta(59Co) range of about 18,000 ppm. The effect of the solvent on delta(59Co) is mostly indirect, resulting primarily from substantial metal-ligand bond contractions on going from the gas phase to the bulk. The simulated solvent effects on geometries and delta(59Co) values are well reproduced by using a polarizable continuum model (PCM), based on optimization and perturbational evaluation of quantum-mechanical zero-point corrections.     

Simulation of 59Co NMR Chemical Shifts in Aqueous Solution

⁵⁹Co chemical shifts were computed at the GIAO‐B3LYP level for [Co(CN)₆]^3?, [Co(H₂O)₆]³⁺, [Co(NH₃)₆]³⁺, and [Co(CO)₄]^? in water. The aqueous solutions were modeled by Car–Parrinello molecular dynamics (CPMD) simulations, or by propagation on a hybrid quantum‐mechanical/molecular‐mechanical Born–Oppenheimer surface (QM/MM‐BOMD). Mean absolute deviations from experiment obtained with these methods are on the order of 400 and 600 ppm, respectively, over a total δ(⁵⁹Co) range of about 18 000 ppm. The effect of the solvent on δ(⁵⁹Co) is mostly indirect, resulting primarily from substantial metal–ligand bond contractions on going from the gas phase to the bulk. The simulated solvent effects on geometries and δ(⁵⁹Co) values are well reproduced by using a polarizable continuum model (PCM), based on optimization and perturbational evaluation of quantum‐mechanical zero‐point corrections.     

Induction of apoptosis by hexaosmium carbonyl clusters

A number of tri- and hexaosmium carbonyl cluster derivatives were screened for cytotoxicity against five cancer cell lines, and the hexaosmium carbonyl clusters Os₆(CO)₁₈ and Os₆(CO)₁₆(NCCH₃)₂ were found to be active against four of these, viz., ER+ breast carcinoma (MCF-7), ER-breast carcinoma (MDA-MB-231), metastatic colorectal adenocarcinoma (SW620) and hepatocarcinoma (Hepg2), with IC₅₀ values as low as 6 μM. Studies on their mode of action with the MDA-MB-231 cell line pointed to the induction of apoptosis, as has been found earlier for the trinuclear cluster Os₃(CO)₁₀(NCCH₃)₂.     

超分子体系中次层相互作用对59Co NMR谱的影响

用＾５０Ｃｏ固体静态ＮＭＲ对〔Ｃｏ（ＣＮ６〕＾３－离子与质子化的大环聚胺阳离子形成的超分子络合物的次层相互作用进行研究,结果表明,氢键的形成对该超分子结构的稳定性起了重要的作用。与仅有静电作用存在的Ｋ３〔ＣｏＣＮ）６〕分子相比,＾５９Ｃｏ的三个化学位移张量的主值差值在超分子体系中明显增大。氢键作用的结果使〔Ｃｏ（ＣＮ６〕３－的对称性发生了改变,导致＾１Ｔ１ｇ三重简并态发生分裂。分裂的大小反映了相互     

异核金属簇合成及催化作用的研究II.钴-铂异核金属簇催化作用的研究

本文报道钴-铂异核金属簇Co~2Pt~2(μ~2-CO)~3(CO)~5(PPh~3)~2对1,3-丁二烯等烯烃的催化性能,表明该异核簇除具有醛化活性之外,还有齐聚环化,加氢和异构化等催化性质.其醛化活性不仅比钴或铂的单核配合物高,而且比该两种配合物的混合物催化剂的活性高.采用X光电子能谱,电子吸收光谱及红外光谱等方法表征钴-铂异核金属簇,并辅以量化计算,试图解释该异核簇的醛化活性较高的原因.     

The reduction of osmium carbonyl clusters by nitriles

The clusters Os₆(CO)₁₈ Os₇(CO)₂₁ and Os₈(CO)₂₃ are reduced to the anoins [Os₆(CO)₁₈]^2?, [Os₇(CO)₂₀]^2? and [Os₈(CO)₂₂]^2?, respectively, by the action of nitriles RCN (R = Me, Et, CH₂C(Me)); the kinetics of the reaction of Os₆(CO)₁₈ with EtCN have been examined and reveal a third order dependence on nitrile concentration.     

Natural abundance 17O NMR spectra of carbonyl metal clusters of the iron triad

¹⁷O NMR spectra (in natural abundance) have been recorded, at room temperature, for a variety of polynuclear iron, ruthenium and osmium carbonyl clusters. Rather sharp linewidths have been observed for stereochemically rigid species, whereas linewidths as large as about 200 Hz have been obtained for fluxional molecules. Even though the observed chemical shift range for terminal CO groups is not very large (about 50 ppm), taking into account linewidths, metal triad and substituent effects have been observed to different extents.     

Enantioseparation of novel chiral heterometal tetrahedral clusters by high-performance liquid chromatography

A series of novel chiral heterometal tetrahedral clusters have firstly been separated on cellulose tris-(3,5-dimethylphenylcarbamate) stationary phase by high-performance liquid chromatography using n-hexane as the mobile phase containing different alcohols as modifiers. The effects of concentration and structures of alcohols in the mobile phases and structures of chiral heterometal tetrahedral clusters on enantioseparation were investigated. The results showed that the concentration and structures of alcohols had large effects on enantioseparation. It also was found that both the metal in the tetrahedral core and the ligand coordinated to the atom in tetrahedral core had significant effects on their chromatographic behavior.     

Non additivity of ligand effects on 59Co NMR chemical shifts in Co(III) complex compounds

⁵⁹Co chemical shift in a number of Co(III) complexes of the type CoA_6-xB_x(x = 0–6, A and B denote corresponding ligators) containing mono- and/or bidentate ligands, was measured. In almost all cases studied it was found that chemical shift appear at lower field than expected on the basis of the Rule on Additivity of Ligand Effects on ⁵⁹Co chemical shift. The non additivity of the ligand effects on ⁵⁹Co chemical shift has been discussed in terms of ligand field theory. It was shown that negative deviations from additivity has to be expected.     

Tetrairidium carbonyl clusters of mono- and di-olefins

The reactions of NEt₄ [Ir₄(CO)₁₁ Br] (I) with mono- and di-olefins in the presence of AgBF₄ gave high yields ( > 90%) of Ir₄(CO)₁₁ (olefin) (II) and Ir4(CO)₁₀(η⁴-diolefin) (III). Oxidation of Ir₄(CO)₁₁ (L = PPh₃, AsPh₃) in the presence of an excess of diolefin by 1 eq. ON(CH₃)₃ gave the clusters Ir₄(CO)₉L(η⁴-diolefin) (IV) and Ir₄(CO)₇L(η⁴-diolefin)₂ (V). Sulphur dioxide quantitatively displaces the monoolefin ligand from II to give Ir₄(CO)₉(μ₂-CO)₂(μ₂-SO₂), which is the first example of a tetrairidium- SO₂ cluster.     

Preparation of doublet, triangular, and tetrahedral colloidal clusters by controlled emulsification

We describe a six-step method for making colloidal clusters of 2, 3, or 4 silica particles with a radius of 1.2 microm. This method, originally described by Manoharan et al. (Manoharan, V. N.; Elsesser, M. T.; Pine, D. J. Science 2003, 301, 483), is based on the encapsulation of silica spheres in emulsion droplets. The originality of our work lies in the preparation of monodisperse emulsions, which allows us to obtain some high yields of small aggregates over a wide range of conditions. Using optical microscopy and disk centrifugation, we show that the relative fractions of 2, 3, and 4 particle aggregates are controlled by the emulsification conditions, particularly the concentration of silica in the dispersed phase. Our best yields are obtained using low to moderate shear rates, a highly viscous continuous phase, and intermediate amounts of silica. The sedimentation of the colloidal solution into a gradient of concentration leads to aqueous suspensions of identical clusters. Since the overall process can easily be scaled up, large quantities of identical clusters may be prepared, which should allow the thermodynamic properties of these new colloidal objects to be measured for the first time. These nonspherical particles could serve as building blocks for more complex assemblies, such as colloidal crystals which could find applications as photonic materials.     

Multitechnique investigation of the physisorption and thermal treatment of mixed-metal clusters on carbon

The three clusters [Ru6PtC(CO)16(COD)] (1), [Ru5PtC(CO)14(COD)] (2) (COD = 1,5-cyclooctadiene), and (NEt4)2[Pd6Ru6(CO)24] (3) were physisorbed onto an active carbon support and used as molecular precursors for supported particles. The samples before and after thermal treatment at 300 degrees C were characterized by a combination of SIMS, XPS, SEM and XRD. It was found that the clusters are molecularly intact, but present in the form of agglomerates on the support at the end of the physisorption step. After thermal treatment, the ligands were lost in all cases, leaving on the surface bimetallic particles containing both starting metals (Ru-Pt in the case of 1 and 2, and Ru-Pd in the case of 3). The presence of the counterion was evidenced for 3, before, but not after, heating. Molecular clusters are thus interesting precursors for the preparation of supported bimetallic phases, and SIMS is the ideal technique to characterize them at each step of their preparation.     

Synthesis and reactivity of sulfido ruthenium carbonyl clusters

A survey of the structures and reactivity of ruthenium carbonyl cluster complexes containing sulfido ligands is presented and discussed.     

Structural stability of boron clusters with octahedral and tetrahedral symmetries

The structural stability of cagelike boron clusters with octahedral and tetrahedral symmetries has been investigated by means of first-principles calculations. Twenty-eight cluster models, ranging from B(10) to B(66), were systematically constructed using regular and semiregular polyhedra as prototypes. The binding energies per atom were, on the whole, slightly lower than those of icosahedral clusters B(80) and B(100), which are supposed to be the most stable in the icosahedral group. The larger clusters did not always have higher binding energies. Isothermal molecular dynamics simulations were performed to determine the deformation temperatures at which clusters began to break or change their structures. We found eight clusters that had nonzero deformation temperatures, indicating that they are in metastable states. The octahedral cluster B(18) had the highest deformation temperature among these, similar to that of icosahedral B(80) and B(100). The analysis of the electronic structure of B(18) showed that it attained this high stability owing to Jahn-Teller distortion.