Two gold-ruthenium clusters derived from Ru3(μ-H)3(μ3-CBr)(CO)9

The reaction between AuMe(PPh₃) and Ru₃(μ-H)₃(μ₃-CBr)(CO)₉ (1) affords the novel heptanuclear cluster Au₄Ru₃(μ₃-CMe)(Br)(CO)₉(PPh₃)₃ (2), containing an Au/Ru₃/Au trigonal pyramidal cluster face-capped by two Au(PPh₃) groups and a CMe ligand, together with Au₂Ru₃(μ-H)(μ₃-CMe)(CO)₉(PPh₃)₂ (3), formed by isolobal replacement of two of the three μ-H atoms in 1 by Au(PPh₃) groups. The latter co-crystallises with the analogous μ₃-CH complex, as also shown spectroscopically.     

Formation of the silylene-bridged complex Fe2(CO)6(μ2-SiCl2)3 from cis-Fe(CO)4(SiCl3)2: an experimental and computational study

Abstract  

Thermolysis of cis-Fe(CO)₄(SiCl₃)₂ results in the formation of the novel compound Fe₂(CO)₆(μ₂-SiCl₂)₃, which was characterized by single crystal X-ray diffraction. Density functional theory calculations were carried out to elucidate possible reaction steps leading to the formation of Fe₂(CO)₆(SiCl₂)₃, including CO dissociation and chlorine abstraction by a SiCl₃ radical generated from homolytic Fe–Si bond cleavage involving a singlet–triplet intersystem crossing.     

Thiolate-bridged heterometallic complexes of manganese and platinum: Synthesis and molecular structures of (CO)4Mn(μ-SPh)Pt(PPh3)2, (CO)3(PPh3)Mn(μ-SPh)Pt(PPh3)(CO), and (CO)3Mn(μ-SPh)Pt(PPh3)(Dppm)

A reaction of the dimer [Mn(CO)₄(SPh)]₂ with (PPh₃)₂Pt(C₂Ph₂) gave the heterometallic complex (CO)₄Mn(μ-SPh)Pt(PPh₃)₂ (I) and its isomer (CO)₃(PPh₃)Mn(μ-SPh)Pt(PPh₃)(CO) (II). A reaction of complex I with a diphosphine ligand (Dppm) yielded the heterometallic complex (CO)₃Mn(μ-SPh)Pt(PPh₃)(Dppm) (III). Complexes I–III were characterized by X-ray diffraction. In complex I, the single Mn-Pt bond (2.6946(3) ?) is supplemented with a thiolate bridge with the shortened Pt-S and Mn-S bonds (2.3129(5) and 2.2900(6) ?, respectively). Unlike complex I, in complex II, one phosphine group at the Pt atom is exchanged for one CO group at the Mn atom. The Mn-Pt bond (2.633(1) ?) and the thiolate bridge (Pt-S, 2.332(2) ?; Mn-S, 2.291(2) ?) are retained. In complex III, the Mn-Pt bond (2.623(1) ?) is supplemented with thiolate (Pt-S, 2.341(2) ?; Mn-S, 2.292(2) 0?) and Dppm bridges (Pt-P, 2.240(1)?; Mn-P, 2.245(2) ?). Apparently, the Pt atom in complexes I–III is attached to the formally double bond , as in Pt complexes with olefins.     

Phenyltellurenyl halide complexes of ruthenium and rhenium (CO)2RuBr2(PhTeBr)2 and (CO)3Re(PhTeI)3(μ3-I): Synthesis and crystal and molecular structures

Reactions of Ru₃(CO)₁₂ with PhTeBr₃ and of Re(CO)₅Cl with PhTeI in benzene give the stable complexes (CO)₂RuBr₂(PhTeBr)₂ (I) and (CO)₃Re(PhTeI)₃(μ³-I) (II) containing two and three ligands PhTeX (X = Br or I), respectively. The bonds between these ligands and the central metal atom are fairly shortened (on average, Ru-Te, 2.608 ?; Re-Te, 2.7554(12)-2.7634(13) ?). The Te-X bonds in the ligands PhTeBr (2.5163(5) ?) and PhTeI (2.7893(15) ?) are not lengthened appreciably. In complex II, the iodide anion is not coordinated by rhenium, yet being attached through weak secondary bonds to three Te atoms of the three ligands PhTeI.     

Synthesis and molecular structure of [((CO)3RuBr2)2(μ-SePh)2Ru(CO)4] cluster with a Ru3Se2 chain core

Treatment of ruthenium carbonyl, [Ru₃(CO)₁₂] with phenylseleno tribromide PhSeBr₃ afforded a new triruthenium cluster, [(CO)₁₀Br₄Ru₃(μ-SePh)₂] (1). Its molecular structure was determined by single crystal XRD method (P2₁/c; a = 10.514(3) Å; b = 10.814(3) Å; c = 19.063(5) Å; β = 105.064(4)°; V = 2093.1(10) Å³) and shown to have two lateral Ru(CO)₃Br₂ units attached via two PhSe bridges to a Ru(CO)₄ center forming a chain-like Ru-Se-Ru-Se-Ru cluster core. This is in contrast with a recently reported reaction of PhTeBr₃ with [Ru₃(CO)₁₂] which formed a monomeric complex of ruthenium-dicarbonyl-dibromo fragment coordinating two PhTeBr ligands, [(CO)₂RuBr₂(PhTeBr)₂].     

Synthesis and crystal structure of new one-dimensional copper(II) complex [Cu4(En)2(μ1,1-N3)4(μ1,1,1-N3)2(μ1,3-N3)2]n

A new polymer azido-bridged copper(II) complex [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂] _n (I) (En = ethylenediamine) has been synthesized and crystallography characterized. Complex I shows one-dimensional coordination polymeric structure based on a tetranuclear cluster unit [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂], in which the azido ions display three different bridging modes.     

对苯二甲酸二丙炔醇酯与Co2(CO)8、Mo2Cp2(CO)4和RuCo2(CO)11的反应

室温下对苯二甲酸二丙炔醇酯分别与Co2CO8Mo2Cp2CO4和RuCo2CO11反应得到三个有机金属化合物C6H4pCO2CH2C2Hμ2Co2CO621、C6H4pCO2CH2C2H2RuCo2CO922和HC2CH2OCOC6H4pCO2CH2C2HμMo2Cp2CO43。研究发现三种金属核对端炔氢的屏蔽作用依次为RuCo2CO9>Co2CO6>Mo2CO4Cp2。化合物1的晶体衍射发现属三斜晶系空间群a=8.1392b=8.8083c=11.3433β=96.2606°V=773.443Z=1Dc=1.748g·cm-3R=0.0513wR=0.1266。     

Novel chromium trinuclear trifluoroacetate complexes Cr3(μ3-O)(CF3COO)6(CH3COOH)2(CF3COO) and Cr3(μ3-O)(CF3COO)6(CH3COOH)2(THF): Synthesis and crystal structure

Novel anhydrous trinuclear ₃-oxo complexes of Cr(III), Cr₃(₃-O)(CF₃COO)₆(CH₃COOH)₂(CF₃COO) (I) and of Cr(III,III,II), Cr₃(₃-O)(CF₃COO)₆(CH₃COOH)₂(THF) (II) (where THF is (CH₂)₄O) are synthesized by anodic dissolution of metallic chromium in solutions of trifluoroacetic acid in acetonitrile and in tetrahydrofuran and their structures are studied by X-ray diffraction analysis. Complex I forms orthorhombic crystals with space group Pna2₁, a = 9.778(1) , b = 16.042(2) , c = 22.851(4) , Z = 4, R ₁ = 0.0332; complex II crystallizes in monoclinic system: space group P2₁/c, a = 9.866(1) , b = 17.895(2) , c = 21.167(4) , = 100.75(2)°, Z = 4, R = 0.0422. The average Cr-(₃-O) distances in compounds I and II are almost equal (1.943(3) and 1.927(3) ). An average length of the Cr-O bond in octahedral surrounding of metal atoms is different in complexes I and II (1.985(4) and 2.003(3) , respectively), which is specified by different oxidation states of the metal atom. The CrCr distances lie in an interval of 3.366(1)–3.337(1) .__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 4, 2005, pp. 266–272.Original Russian Text Copyright © 2005 by Glazunova, Boltalin, Troyanov.     

Synthesis,structure characterization and thermal properties of [Zr6(μ3-O)4(μ3-OH)4(OOCCH2Bu)9(μ2-OH)3]2

Oxo/hydoxo zirconium(IV) complex of the general formula [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉(μ₂-OH)₃]₂ has been isolated, when Zr(OⁱPr)₄ reacted with a 2-fold excess of 3,3-dimethylbutyric acid. Single crystal X-ray diffraction data, collected at 103 and 153 K, showed that the studied compound crystallizes in hexagonal system (P6₃/m (no. 176)). Structure consists of dimers composed of [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉] sub-units, linked by six μ₂-OH bridges. Infrared spectroscopic studies proved the presence of hydroxo groups in the structure of studied clusters and formation of different types of oxo/hydroxo bridges. The application of variable temperature infrared spectroscopy and differential scanning calorimetry revealed that the structure of this complex undergoes the phase transitions at 143–183 and 203–293 K. Comparison of spectral and crystallographic data suggests that these phase transitions might be related to changes in the strength of Zr–O bonds of μ₂-OH bridges linking complex sub-units, and change in symmetry of the crystal lattice (from hexagonal to trigonal). Analysis of thermogravimetric data showed that decomposition of [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉(μ₂-OH)₃]₂ proceeds with complete conversion to ZrO₂ (monoclinic form) between 603 and 803 K.     

Unsaturation in binuclear cyclopentadienylchromium carbonyl thiocarbonyls: Viability of (η-C5H5)2Cr2(CS)2(CO)3 in contrast to (η-C5H5)2Cr2(CO)5

The cyclopentadienylchromium carbonyl thiocarbonyls Cp₂Cr₂(CS)₂(CO)_n (n = 4, 3, 2, 1) have been studied by density functional theory using the B3LYP and BP86 functionals. The lowest energy Cp₂Cr₂(CS)₂(CO)₄ structure can be derived from the experimentally characterized unbridged Cp₂Cr₂(CO)₆ structure by replacing the two terminal carbonyl groups furthest from the Cr-Cr bond with two terminal CS groups. The two lowest energy Cp₂Cr₂(CS)₂(CO)₃ structures have a single four-electron donor η²-μ-CS group and a formal Cr-Cr single bond of length ∼3.1 Å. In contrast to the carbonyl analogue Cp₂Cr₂(CO)₅ these Cp₂Cr₂(CS)₂(CO)₃ structures are viable with respect to disproportionation into Cp₂Cr₂(CS)₂(CO)₄ and Cp₂Cr₂(CS)₂(CO)₂ and thus are promising synthetic targets. The lowest energy Cp₂Cr₂(CS)₂(CO)₂ structures have all two-electron donor CO and CS groups and short CrCr distances around ∼2.3 Å suggesting the formal triple bonds required to give the chromium atoms the favored 18-electron configurations. These Cp₂Cr₂(CS)₂(CO)₂ structures are closely related to the known structure for Cp₂Cr₂(CO)₄. In addition, several doubly bridged structures with four-electron donor η²-μ-CS bridges are found for Cp₂Cr₂(CS)₂(CO)₂ at higher energies. The global minimum Cp₂Cr₂(CS)₂(CO) structure is a triply bridged triplet with a CrCr triple bond (2.299 Å by BP86). A higher energy singlet Cp₂Cr₂(CS)₂(CO) structure has a shorter Cr-Cr distance of 2.197 Å (BP86) suggesting the formal quadruple bond required to give each chromium atom the favored 18-electron configuration.     

Reaction of the heteronuclear cluster RuOs3(μ-H)2(CO)13 with toluene

The heteronuclear cluster RuOs₃(μ-H)₂(CO)₁₃ (4) reacts with refluxing toluene to form the clusters Ru₂Os₃(μ-H)₂(CO)₁₆ (5) RuOs₃(CO)₉(μ-CO)₂(η⁶-C₆H₅Me) (6) and Ru₂Os₃(CO)₁₂(μ-CO)(η⁶-C₆H₅Me) (7). Cluster 5 exists as a mixture of five isomers. The inter-relationship among the clusters has also been investigated.     

Reactivity of the heteronuclear cluster RuOs3(μ-H)2(CO)13 with indene

The heteronuclear cluster RuOs₃(μ-H)₂(CO)₁₃ (1) reacts with indene under thermal activation to afford the novel clusters RuOs₃(μ-H)(CO)₉(μ-CO)₂(η⁵-C₉H₇) (3), RuOs₃(μ-H)(CO)₉(μ₃,η⁵:η²:η²-C₉H₇) (4) and Ru₂Os₃(μ-H)(CO)₁₁(μ₃,η⁵:η²:η²-C₉H₇) (5), the latter two possessing indenyl ligands in the μ₃,η⁵:η²:η² bonding mode. Cluster 5 exists as a mixture of two isomers. The inter-relationship among the clusters has also been investigated.     

Ditertiary phosphine derivatives of the heteronuclear cluster RuOs3(μ-H)2(CO)13

The heteronuclear cluster RuOs₃(μ-H)₂(CO)₁₃ (1) reacted readily with a number of ditertiary phosphines under chemical activation with trimethylamine-N-oxide. The solid-state and solution structures of these derivatives have been examined. Six structural types have been characterized crystallographically, including one in which a phenyl group migrates from the ditertiary phosphine ligand to the metal framework. There are many more isomers present in solution, most of which are rapidly inter-converting via hydride migrations.     

Reactivity of [Os3(CO)10(NCMe)2] and [Os3(CO)10(μ-Cl)(μ-AuPPh3)] with 4-mercaptopyridine: X-ray structure of [Os3(CO)10(μ-H)(μ-SC5H4N)] and [Os3(CO)10(μ-AuPPh3)(μ-SC5H4N)]

The compound [Os₃(CO)₁₀(μ-Cl)(μ-AuPPh₃)] (2) was prepared from the reaction between [Os₃(CO)₁₀(NCMe)₂] (1) and [AuClPPh₃] under mild conditions. The reaction of 2 with 4-mercaptopyridine (4-pyS) ligand yielded compounds [Os₃(CO)₁₀(μ-H)(μ-SC₅H₄N)] (4), formed by isolobal replacement of the fragment [AuPPh₃]⁺ by H⁺ and [Os₃(CO)₁₀(μ-AuPPh₃)(μ-SC₅H₄N)] (5). [Os₃(CO)₁₀(μ-H)(μ-SC₅H₄N)] (4) was also obtained by substitution of two acetonitrile ligands in the activated cluster 1 by 4-pyS, at room temperature in dichloromethane. Compounds 2-5 were characterized spectroscopically and the molecular structures of 4 and 5 in the solid state were obtained by single crystal X-ray diffraction studies.     

Synthesis and crystal structure of [W3S4(Acac)3(PPh3)3]PF6 · 0.5CHCl3 and [W3S4(Hfac)3(PPh3)2Br] · 2CHCl3

New cluster complexes [W₃S₄(Acac)₃(PPh₃)₃]PF₆ · 0.5CHCl₃ (Acac = CH₃C(O)CHC(O)CH₃) (I) and [W₃S₄(Hfac)₃(PPh₃)₂Br] · 2CHCl₃ (Hfac = CF₃C(O)CHC(O)CF₃) (II) were synthesized. Their molecular and crystal structures were determined by X-ray diffraction. The cis-cis type of coordination of acetylacetonate and hexafluoroacetylacetonate ligands in I and II, respectively, was established, and the PPh₃ ligands were found in the trans-positions with respect to the “capping” sulfide ligand (μ³-S).     

Synthesis and structural characterisation of the palladium N-heterocyclic carbene cluster complexes [Pd3(μ-CO)3(NHC)3] and [Pd3(μ-SO2)3(NHC)3]

The reduction of trans-[Pd(NHC)₂Cl₂] (NHC = IMes, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; IⁱPr₂ = 1,3-bis-isopropylimidazol-2-ylidene) with potassium graphite under an atmosphere of CO affords the palladium NHC carbonyl clusters [Pd₃(μ-CO)₃(NHC)₃] (NHC = IMes, 1; IⁱPr₂, 3). Treatment of 1 with SO₂ at room temperature yields the bridging SO₂ complex [Pd₃(μ-SO₂)₃(IMes)₃] (4) in quantitative yield. Complexes 1, 3 and 4 have been structurally characterised by X-ray crystallography.     

Double complex salts [Pd(NH3)4]3[Rh(NO2)6]2, [Pd(NH3)4]3[Rh(NO2)6]2·H2O as promising precursors to prepare Pd-Rh nanoalloys

Two new double complex salts [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂ (I) and [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂·H₂O (II) are synthesized and characterized. The techniques to produce one-phase residues of the salts are developed. The crystallographic data for I: a = 18.915(2) ?, V = 6767.4 ?³, F-43c space group, Z = 8, d _x = 2.548 g/cm³; II: a = 21.160(6) ?, b = 8.085(7) ?, c = 21.363(4) ?, β = 91.71(4)°, V = 3661.1(6) ?³, P2₁/c space group, d _x = 2.357 g/cm³. Thermal properties of the obtained compounds in the hydrogen and helium atmosphere are studied. It is shown that the final product of their decomposition both in the inert and reducing atmosphere is a powder consisting of bimetallic nanosized particles (nanoalloy) of Pd_0.59Rh_0.41 (Fm-3m space group, a = 3.856(2) ?, crystallite size of 8–11 nm).     

Li3V2(PO4)3/C和Li2.5Na0.5V2(PO4)3/C的结构和电化学性能的比较研究

采用溶胶-凝胶法合成了锂离子正极材料Li3V2(PO4)3/C(LVP/C)及Li2.5Na0.5V2(PO4)3/C,并用XRD、循环伏安及交流阻抗等方法,研究了大量Na+掺杂对材料结构和电化学性能影响。结果表明,大量钠离子的掺杂会使LVP结构由单斜向菱方转变。掺杂化合物Li2.5Na0.5V2(PO4)3/C在0.5 C充电1 C放电时,首次放电容量为118 mAh.g-1,50次循环后容量保持率为92.4%,并发现与单斜LVP存在多个放电平台不同,Li2.5Na0.5V2(PO4)3/C仅在3.7 V处有一个放电平台。     

Cu(NO3)2(La(NO3)3)-CO(NH2)2-H2O三元体系的等温溶度研究

本文首次报道三元体系Cu(NO₃)₂-CO(NH₂)₂-H₂O(30℃)和La(NO₃)₃-CO(NH₂)₂-H₂O(25℃)的等温溶度及饱和溶液、折光率,绘制相应的溶度图及折光率-组成图。体系中发现有组成为Cu(NO₃)₂·4CO(NH相似文献   

Fe(CO)5 promoted C-S bond activation and formation of an unusual C2S3 ligand in [{Fe2(CO)6}2(μ-C2S3)]

Photolysis of a hexane solution containing Fe(CO)₅ and CS₂ leads to desulfurization and formation of a novel cluster [{Fe₂(CO)₆}₂(μ-C₂S₃)] (1). Its molecular structure was determined by single crystal X-ray diffraction methods and shown to consist of two distinct Fe₂(CO)₆ units linked by an unusual C₂S₃ unit.