A family of calix[4]arene-supported [Mn(III)2Mn(II)2] clusters

In the cone conformation calix[4]arenes possess lower-rim polyphenolic pockets that are ideal for the complexation of various transition-metal centres. Reaction of these molecules with manganese salts in the presence of an appropriate base (and in some cases co-ligand) results in the formation of a family of calixarene-supported [Mn(III)(2)Mn(II)(2)] clusters that behave as single-molecule magnets (SMMs). Variation in the alkyl groups present at the upper-rim of the cone allows for the expression of a degree of control over the self-assembly of these SMM building blocks, whilst retaining the general magnetic properties. The presence of various different ligands around the periphery of the magnetic core has some effect over the extended self-assembly of these SMMs.     

二维配位聚合物[Mn(FA)2(4，4′-bipy)]n的合成、晶体结构及量子化学研究

A novel manganese coordination polymer [Mn(FA)₂(4，4′-bipy)]_n(HFA=2-furancarboxylic acid, 4,4′-bipy=4,4′-bipyridine) has been synthesized by hydrothermal methods. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group C2/c with a=1.698 4(3) nm, b=1.168 6(2) nm, c=1.009 5(17) nm, β=109.455(11)°, V=1.889 2(6) nm³, Z=4, D_c=1.523 g·cm^-3, M_r=433.27, F(000)=884, μ=0.740 mm^-1, R₁=0.028 2 and wR₂=0.071 0. In the crystal, the manganese atom is six-coordinated by two nitrogen atoms from 4,4′-bipyridine and four oxygen atoms from furancarboxylic acid molecules, completing an octahedral geometry. The 4,4′-bipyridine molecules are connected to the infinite chain [Mn(FA)₂]_n to form a two-dimensional layer. The quantum chemistry calculation on the title complex has been performed by means of G98W package and taking Lanl2dz basis set. CCDC: 296763.     

二维配位聚合物[Mn(FA)_2(4,4''''-bipy)]_n的合成、晶体结构及量子化学研究

配位聚合物通常是通过某种有机配体与金属的配位几何选择以及无限网络的拓扑结构控制而形成的具有无限结构的化合物[1],其结构新颖并具有不寻常的光电效应、非线性光学性能、磁性、超导及催化等诸多具有诱人应用前景的独特性能。因此,近二十多年来倍受化学家和材料学家的重视[2     

Mononuclear and dinuclear complexes with a [Ru(tBu2PCH2CH2PtBu2)(CO)] core

Thermolysis of solid [Ru(d(t)bpe)(CO)2Cl2](2, d(t)bpe =(t)Bu2PCH2CH2P(t)Bu2) under vacuum affords the five-coordinate complex [Ru(d(t)bpe)(CO)Cl2] (4), which was shown by X-ray crystallography to contain a weak remote agostic interaction. In solution, 4 can be readily trapped by CO, CH3CN or water to give [Ru(d(t)bpe)(CO)(L)Cl2](L = CO, 2; L = CH3CN, 6; L = H2O, 7). Reaction of 4 with AgOTf/H2O yields the tris-aqua complex [Ru(d(t)bpe)(CO)(H2O)3](OTf)2 (8), which has been structurally characterised and probed in solution by pulsed-gradient spin echo (PGSE) NMR spectroscopy. The water ligands in 8 are labile and easily substituted to give [Ru(d(t)bpe)(CO)(NCCH3)3](OTf)2 (10) and [Ru(d(t)bpe)(CO)(DMSO)3](OTf)2 (11). In the presence of CO, the tris-aqua complex undergoes water-gas shift chemistry with formation of the cationic hydride species [Ru(d(t)bpe)(CO)3H](OTf) (12) and CO2. X-Ray crystal structures of complexes 2, 4, 6, 8 and 11-12 are reported along with those for [{Ru(d(t)bpe)(CO)}2(mu-Cl)2(mu-OTf)](OTf) (3), [{Ru(d(t)bpe)(CO)}2(mu-Cl)3][Ru(d(t)bpe)(CO)Cl3](5) and [Ru(d(t)bpe)(CO)(H2O)2(OTf)](OTf)(9).     

Synthesis and crystal structure of a novel two-dimensional network complex [Mn(O_2CCH_2Cl)_2(phen)]_n

A novel two-dimensional network manganese(Ⅱ) polymer complex [Mn(O2CCH2CI)2-(phen)]n has been synthesized and characterized by elemental analysis and IR spectrum. The crystal structure of title complex has also been determined, which is in monoclinic of a space group P21/c with the following unit cell parameters at 294K: a =1.9738(4) nm, b =1.1384(2) nm, c =0.74915(14) nm, V=1.6795(5) nm3, Z= 2.     

Crystal Structure and Magnetic Property of a Two-dimensional Manganese Compound [Mn(PhCOO)_2(4,4'-bipyridine)]_n

A new two-dimensional polymeric manganese compound [Mn(PhCOO)2(4,4'-bi-pyridine)]n 1 has been prepared and structurally characterized by X-ray diffraction. The complex crystallizes in space group Pbcn with a = 18.7158(2), b = 11.6919(3), c = 9.4799(2) , V = 2074.42(7) 3, Z = 4, Mr = 453.34, Dc = 1.452 g/cm3, μ = 0.670 mm-1 and F(000) = 932. The final refinement gave R = 0.0458 and wR = 0.1439 for 1358 observed reflections with I > 2σ(I). The complex consists of repeating units of Mn(PhCOO)2(4,4'-bipyridine). Each Mn center is six-coordinated by four carboxylate O atoms of four benzoate anions and two pyridyl N atoms from bipy ligands to furnish a slightly distorted octahedral geometry. The two adjacent Mn atoms are connected by a pair of μ1,3-carboxylate groups to form infinite chains, which are further interlinked by bipy to complete a 2D grid network. The magnetic property of the polymeric complex has also been investigated.     

Synthese und Strukturbestimmung von (tBuP)4Sn(CH3)2 und (CH3)2Sn[(tBu)P?P(tBu)]2Sn(CH3)2

Synthesis and Structure Analysis of (tBuP)₄Sn(CH₃)₂ and (CH₃)₂Sn[(tBu)P? P(tBu)]₂Sn(CH₃)₂ The diphosphides K₂[(tBu)P? (tBuP)₂? P(tBu)] 7 or K₂[(tBu)P? P(tBu)] 8 react with (CH₃)₂SnCl₂ in a molar ratio of 1 : 1 to form the binary 5-membered ring system P₄Sn 4 a and the 6-membered ring system Sn(P₂)₂Sn 5 a respectively. When (CH₃)₂SnCl₂, however, is treated with 8 in a molar ratio of 2 : 1 the 4-membered ring system P₃Sn 2 a is formed which includes the fragmentation of the intermediate K₂[(CH₃)₂Sn ((tBu)P? P(tBu))₂] 9. 4 a and 5 a could be obtained in a pure form and characterized NMR spectroscopically and by X-ray structure analyses; 2 a was identified only NMR spectroscopically.     

Synthesis and Crystal Structures of Two Complexes [Mn2(L)2(H2bta)2(H2O)]n and[Cu2(L)(H2bta)0.5(H2O)]n

Two new complexes, [Mn₂(L)₂(H₂bta)₂(H₂O)]_n ( 1 ) and [Cu₂(L)(H₂bta)_0.5(H₂O)]_n ( 2 ) (H₄bta=1,2,4,5‐benzene‐tetracarboxylic acid, L=imidazo[4,5‐f][1,10]phenathroline) were prepared under hydrothermal conditions and their structures determined by single‐crystal X‐ray diffration. The X‐ray diffraction reveals that complex 1 , consisting of two crystallographically independent fragments A1 and A2, displays an interesting 3D supramolecular network constructed with ABAB sequence through hydrogen bonding interactions. In complex 2 , the copper atoms connected by the H₂bta^2? ligands, the chains also are assembled into a 3D honeycomb configuration network formed by moleculars and aromatic π‐π stacking interactions.     

一个锰(Ⅲ)Schiff碱配合物[Mn(napn)(CH_3OH)_2]ClO_4的合成与晶体结构

合成了一个新配合物[Mn(napn)(CH3OH)2]ClO4 (C26H26 Cl N2O8Mn,Mr = 584.88,H2napn = 双a-萘酚醛缩乙二胺),并测定了其晶体结构。晶体属于三斜晶系,空间群P ,a = 7.813(1),b = 13.025(2),c = 14.089(2) ? = 64.89(3), = 83.98(3), = 78.11(3)海琕 = 1270.16 ?,Z = 2, Dc = 1.529 g/cm3, F(000) = 604, R = 0.0837, wR = 0.1636。锰(Ⅲ)离子的配位构型为拉长的八面体。Schiff碱配体napn2-中的N2O2在赤道平面与锰(Ⅲ)形成四配位,2个CH3OH中的O原子分别在赤道平面两侧轴向位置与锰(Ⅲ)配位。由于Jahn-Teller效应,轴向上的MnO平均键长为2.52 拧A硗猓О写嬖诜肿幽诤头肿蛹淝饧?     

Probing Surface Sites of TiO2: Reactions with [HRe(CO)5] and [CH3Re(CO)5]

Two carbonyl complexes of rhenium, [HRe(CO)₅] and [CH₃Re(CO)₅], were used to probe surface sites of TiO₂ (anatase). These complexes were adsorbed from the gas phase onto anatase powder that had been treated in flowing O₂ or under vacuum to vary the density of surface OH sites. Infrared (IR) spectra demonstrate the variation in the number of sites, including Ti⁺³? OH and Ti⁺⁴? OH. IR and extended X‐ray absorption fine structure (EXAFS) spectra show that chemisorption of the rhenium complexes led to their decarbonylation, with formation of surface‐bound rhenium tricarbonyls, when [HRe(CO)₅] was adsorbed, or rhenium tetracarbonyls, when [CH₃Re(CO)₅] was adsorbed. These reactions were accompanied by the formation of water and surface carbonates and removal of terminal hydroxyl groups associated with Ti⁺³ and Ti⁺⁴ ions on the anatase. Data characterizing the samples after adsorption of [HRe(CO)₅] or [CH₃Re(CO)₅] determined a ranking of the reactivity of the surface OH sites, with the Ti⁺³? OH groups being the more reactive towards the rhenium complexes but the less likely to be dehydroxylated. The two rhenium pentacarbonyl probes provided complementary information, suggesting that the carbonate species originate from carbonyl ligands initially bonded to the rhenium and from hydroxyl groups of the titania surface, with the reaction leading to the formation of water and bridging hydroxyl groups on the titania. The results illustrate the value of using a family of organometallic complexes as probes of oxide surface sites.     

邻二氮菲苯妥英合锰(Ⅱ)三元配合物的合成、结构与抗微生物活性研究

The title complex [Mn(pht)₂(phen)] (Hpht=5，5-diphenylimidazoline-2，4-dione， phen=1，10-phenanthroline) was synthesized and characterized by elemental analysis， IR and X-ray diffraction single-crystal structure analysis. The compound crystallizes in the monoclinic system， space group C2/c with a=2.631 5(16) nm， b=0.924 5(6) nm， c=1.550 8(10) nm， β=116.231(7)°; V=3.384(4) nm³，M_r=737.66， Z=4， F(000)=1 524， D_c=1.448 g·cm^-3， μ=0.446 mm^-1， the final R=0.069 9 and wR=0.195 3. The complex was valued for its antimicrobial activity against some bacteria in vitro. It was found to be active against the four test bacterial organisms. CCDC: 616309.     

Unsaturated Ru(0) species with a constrained bis-phosphine ligand: [Ru(CO)2(tBu2PCH2CH2PtBu2)]2. Comparison to [Ru(CO)2(PtBu2Me)2

The synthesis of Ru(C2H4)(CO)2(dtbpe) (dtbpe = tBu2PC2H4PtBu2), then green [Ru(CO)2(dtbpe)]n is described. In solution, n = 1, while in the solid state, n = 2; the dimer has two carbonyl bridges. DFTPW91, MP2, and CCSD(T) calculations show that the potential energy surface for bending one carbonyl out of the RuP2C(O) plane is essentially flat. Ru(CO)2(dtbpe) reacts rapidly in benzene solution to oxidatively add the H-E bond of H2, HCl, HCCR (R = H, Ph), [HOEt2]BF4, and HSiEt3. The H-C bond of C6HF5 oxidatively adds at 80 degrees C. CO adds, as does the C=C bond of H2C=CHX (X = H, F, Me). The following do not add: N2, THF, acetone, H3COH, and H2O.     

多面体低聚八氨基苯基硅倍半氧烷合成方法改进及其表征

以八硝基苯基硅倍半氧烷(ONPS)为原料, 5% Pd/C 和FeCl₃ 为催化剂, 水合肼为还原剂, 在四氢呋喃溶液中反应 1 h 合成了八氨基苯基硅倍半氧烷(OAPS). 相比文献中已有的其它合成方法, 该方法合成过程简单且稳定, 催化效率高、产率高、周期短. 通过FTIR, ¹H NMR, GPC 对产物进行了表征, 证明了硝基已完全转化. 通过催化剂的控制, 分离出ONPS 向OAPS 转化过程中的一种含有羟胺和二羟胺基团的中间体. 分析了OAPS 合成机理, 提出了ONPS 和水合肼的反应历程. 认为ONPS 中的硝基先经过2 电子转移转化为二羟胺化合物, 然后经过脱水加氢生成羟胺化合物, 最后再经过脱水加氢生成OAPS; 在有ONPS 存在的情况下, 水合肼主要转化为氮气和氢气, 待ONPS 完全转化为OAPS 后, 水合肼转化为氮气和氨气.     

Synthesis and Crystal Structure of a New Three-dimensional Coordination Polymer： [Mn（2,3- pdc） （H2O）]n （2,3-pdc = Pyridine-2,3-dicarboxylate）

A new three-dimensional coordination polymer [Mn（2,3-pdc）（H20）]n （2,3-pdc = pyridine-2,3-dicarboxylate） 1 has been hydrothermally synthesized and structurally characterized. The crystal belongs to the monoclinic system, space group P21/c with a = 6.4168（5）, b = 10.7939（9）, c = 11.1549（10） A, β = 94.733（4）°, V = 769.98（11） A3, Z = 4, Mr = 238.06, De = 2.054 g/cm3, μ（MoKa） = 1.707 mm-1, F（000） = 476, Rint = 0.0326; R = 0.0499 and wR = 0.1636 for 1564 observed reflections with I 〉 2σ（I）. X-ray diffraction analyses reveal that the title compound is a three-dimensional coordination polymer consisting of one MnⅡ center with a distorted octahedral environment arranged by four 2,3-pdc ligands and one water molecule.     

Amorphous silica as a versatile supermolecular ligand for Ni(II) amine complexes: toward interfacial molecular recognition.

Selective adsorption of Ni(II) amine complexes used as precursors for supported catalysts was studied on amorphous silica surfaces. The nature of the adsorption sites was probed by [Ni(en)(dien) (H2O)]2+, [Ni(en)2(H2O)2]2+, and [Ni(dien)(H2O)3]2+ (en = ethylenediamine, dien = diethylenetriamine), which respectively contain one, two, and three labile aqua ligands. The silica surface acts as a mono- or polydentate ligand that can substitute the aqua ligands of the Ni(II) complexes in an inner-sphere adsorption mechanism. Room-temperature adsorption isotherms indicate that each nickel complex selects a limited number of adsorption sites; different sites are recognised by the three complexes, even though they have the same charge and comparable sizes. Several spectroscopic techniques (UV/Vis/NIR, EXAFS, and 29Si NMR) were used to confirm the selective character of the interaction of Ni(II) amine complexes with the silica surface. The specific sites include both silanol/silanolate groups in the same number as the original labile ligands and other surface groups that probably act as hydrogen-bond acceptors. These two types of groups cooperate to result in interfacial molecular-recognition phenomena with interactional complementarity.     

Understanding the reactivity of [WNAr(CH2tBu)2(CHtBu)] (Ar = 2,6-iPrC6H3) with silica partially dehydroxylated at low temperatures through a combined use of molecular and surface organometallic chemistry

Reaction of [WNAr(CH₂tBu)₂(CHtBu)] (Ar = 2,6-iPrC₆H₃) with silica partially dehydoxylated at 200 °C does not lead only to the expected bisgrafted [(SiO)₂WNAr(CHtBu)] species, but also surface reaction intermediates such as [(SiO)₂WNAr(CH₂tBu)₂]. All these species were characterized by infrared spectroscopy, 1D and 2D solid state NMR, elemental analysis and molecular models obtained by using silsesquioxanes. While a mixture of several surface species, the resulting material displays high activity in the olefin metathesis.