Synthesis, Characterization and Crystal Structure of [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2]

The reaction of μ-alkyne-bridged dimolybdenum compound [Mo2(μ-C2HPh)(CO)4(η5-C5H4C(O)Me)2] 1 with Co2(CO)8 in refluxing toluene gave a new butterfly compound [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2] 2 which was fully characterized by elemental analysis, IR, 1H NMR and X-ray single crystal diffraction techniques. 2 crystallized in monoclinic system, C30H20Co2Mo2O10, Mr=850.23, space group P21/a(#14), a=14.165(5), b=12.498(2), c=16.204(2)(A), β = 96.50(2)°, V = 2850(1)(A)3, Z = 4, Dc = 1.981 g cm-3, F(000)=1672, μ(MoKα)=20.41 cm-1, final R=0.030, Rw=0.039 for 4831 observable reflections with I>2σ(I). The structure contains a Co2Mo2 butterfly core, and each Mo-Co bond is spanned by an asymmetric semi-bridging carbonyl ligand.     

The preparation of a series of ring-linked derivatives of [Fe2(η-C5H5)2(CO)2(μ-CO)2] starting from [Fe2η5,η5-C5H4CH(NMe3)CH(NMe2)C5H4}(CO)2(μ-CO)2]+ salts

The salts [Fe₂η⁵,η⁵-C₅H₄CH{NMe₃)CH(NMe₂)C₅H₄}(CO)₂(μ-CO)₂][X] (X = I or SO₃CF₃) are the synthetic precursors to a wide range of [Fe₂(η-C₅H₅)₂(CO)₂(μ-CO)₂] derivatives in which the two cyclopentadienyl ligands are joined by a two-carbon bridge.     

Synthesis and structures of the η5-C5H5Cl(CO)2W-η1,η5-(PPh2)C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3 and MeSi[C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)2PPh3]3 complexes

The metallation of the η⁵-C₅H₅(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃ complex with BuⁿLi (THF, ?78 °C) followed by the treatment of the lithium derivative with Ph₂PCl afforded the η⁵-Ph₂PC₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃ complex. The reaction of the latter with η⁵-C₅H₅(CO)₃WCl in the presence of Me₃NO produced the trinuclear complex η⁵-C₅H₅Cl(CO)₂W-η¹,η⁵-(Ph₂P)C₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃. The structure of the latter complex was established by IR, UV, and 1H and ³¹P NMR spectroscopy and X-ray diffraction. The reaction of MeSiCl₃ with three equivalents of LiC₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₂PPh₃ gave the hexanuclear complex MeSi[C₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₂PPh₃]₃.     

Rh2(CO)4(μ-Cl)2和Rh4(μ-CO)3(CO)4的简正振动分析

金属簇合物具有独特的结构和成键方式。本文对铑簇合物的简正振动分析进行了研究。通过红外光谱用石蜡油糊涂KBr和聚乙烯窗口, 在Nicolet 200SXV FT-IR光谱上测定了Rh2(CO)4(μ-Cl)2的构型, 并使用分子振动全分析程序MVTA(Basic语言), 在PC机上进行计算。     

Synthesis,Characterization and Crystal Structure of〔Co_2Mo_2(μ-_4-C_2HPh)(μ-CO)_4(CO)_4(η~-5C_5H_4C(O)Me)_2〕

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Synthesis and structural characterization of the first transition metal cluster containing a PPh2AuPPh3 ligand,Ir4(CO)8(μ-CO)3(PPh2AuPPh3), and its conversion into Ir4(CO)9(μ-CO)(μ-PPh2)(μ-AuPPh3)

Deprotonation of Ir₄(CO)₁₁PPh₂H (1) in the presence of [AuPPh₃][PF₆] yields the novel species Ir₄(CO)₁₁(PPh₂AuPPh₃) (2), which possesses a tetrahedral framework bearing a terminally bound PPh₂AuPPh₃ ligand. When heated in toluene, 2 is converted into the phosphido species Ir₄(CO)₁₀(μ-PPh₂)(μ-AuPPh₃).     

Synthesis and crystal structure of [(η3-C3H5)(CO)2Mo(μ-S2CPCy3)-Mo(η3-CH2CMeCH2)(CO)2]

A novel dimolybdenum complex [(³-C₃H₅)(CO)₂Mo(-S₂CPCy₃)Mo(³-CH₂CMeCH₂)(CO)₂], obtained by reacting the [(CO)₂(³-C₃H₅)Mo(-S₂CPCy₃)Mo(CO)₃]^– anion with an excess of ClCH₂CMe=CH₂, has been characterized by i.r., ³¹P{¹H}, ¹H- and ¹³C-n.m.r. spectroscopy and by elemental analysis. The crystal structure of the complex, determined by X-ray diffraction, shows a definite preference for the central carbon of the S₂CPCy₃ bridge to bind to the Mo(2) atom coordinated by ³-2-methylallyl, rather than the Mo(1) atom attached to unsubstituted ³-allyl ligand.     

CRYSTAL STRUCTURE OF MIXED-METAL CLUSTER(η~5-C_5H_5)_2Mo_2Fe_2(μ3-S)_2(μ-CO)_2(CO)_6

<正> Mr= 721.98,monoclinic, P21/n,a= 9.773(1), b = 6.641(3), c = 16.258(1)A,β=92.25(1)°,V=1054.4(7)A3,Dx = 2.274g/cm3,Z=2,λ(MoKα)=0.7107A.Final R= 0.024,Rw= 0.036 for 1554 observed reflections. The cluster core Fe2Mo2 is a rhombic plane with Mo-No distance of 2.827A and average Mo-Fe distance of 2.773A.     

The insertion of acetylene into the formal ruthenium-phosphorus bonds of closo-[Ru4(μ4-PPh)2(μ2-CO)(CO)10. Crystal structure of [Ru4(μ4-PPh){μ4-η3-P(Ph)CHCH}(μ2-CO)(CO)10]

Treatment of closo-[Ru₄(μ₄-PPh)₂(μ₂-CO)(CO)₁₀] with acetylene under ambient conditions leads to the insertion of the acetylene into the skeletal framework of the cluster and the formation of [Ru₄(μ₄-PPh){μ₄-η³-P(Ph)CHCH}(μ₂-CO)(CO)₁₀], the structure of which has been determined X-ray crystallographically.     

Comparison of the Bonding of Benzene and C60 to a Metal Cluster: Ru3(CO)9(μ3-η2,η 2,η2-C6H6) and Ru3(CO)9(μ3-η2,η2,η2-C60)

The electron distributions and bonding in Ru₃(CO)₉( ³- ², ², ²-C₆H₆) and Ru₃(CO)₉( ³- ², ², ²-C₆₀) are examined via electronic structure calculations in order to compare the nature of ligation of benzene and buckminsterfullerene to the common Ru₃(CO)₉ inorganic cluster. A fragment orbital approach, which is aided by the relatively high symmetry that these molecules possess, reveals important features of the electronic structures of these two systems. Reported crystal structures show that both benzene and C₆₀ are geometrically distorted when bound to the metal cluster fragment, and our ab initio calculations indicate that the energies of these distortions are similar. The experimental Ru–C_fullerene bond lengths are shorter than the corresponding Ru–C_benzene distances and the Ru–Ru bond lengths are longer in the fullerene-bound cluster than for the benzene-ligated cluster. Also, the carbonyl stretching frequencies are slightly higher for Ru₃(CO)₉( ³- ², ², ²-C₆₀) than for Ru₃(CO)₉( ³- ², ², ²-C₆H₆). As a whole, these observations suggest that electron density is being pulled away from the metal centers and CO ligands to form stronger Ru–C_fullerene than Ru–C_benzene bonds. Fenske-Hall molecular orbital calculations show that an important interaction is donation of electron density in the metal–metal bonds to empty orbitals of C₆₀ and C₆H₆. Bonds to the metal cluster that result from this interaction are the second highest occupied orbitals of both systems. A larger amount of density is donated to C₆₀ than to C₆H₆, thus accounting for the longer metal–metal bonds in the fullerene-bound cluster. The principal metal–arene bonding modes are the same in both systems, but the more band-like electronic structure of the fullerene (i.e., the greater number density of donor and acceptor orbitals in a given energy region) as compared to C₆H₆ permits a greater degree of electron flow and stronger bonding between the Ru₃(CO)₉ and C₆₀ fragments. Of significance to the reduction chemistry of M₃(CO)₉( ³- ², ², ²-C₆₀) molecules, the HOMO is largely localized on the metal–carbonyl fragment and the LUMO is largely localized on the C₆₀ portion of the molecule. The localized C₆₀ character of the LUMO is consistent with the similarity of the first two reductions of this class of molecules to the first two reductions of free C₆₀. The set of orbitals above the LUMO shows partial delocalization (in an antibonding sense) to the metal fragment, thus accounting for the relative ease of the third reduction of this class of molecules compared to the third reduction of free C₆₀.     

SYNTHESIS,CHARACTERIZATION AND CRYSTAL STRUCTURES OF η~5-CH_3C_5H_4)M(CO)_2NO AND(η~5-CH_3C_5H_4)M(μ_3-NH)(μ_2-NO)(μ_2-CO)Fe_2(CO)_6(M=Mo or W)

Synthesis of complexes(η~5-CH_3C_5H_4)M(CO)_2NO(M=Mo,I;M=W,II)and clusters(η~5-CH_3C_5H_4)M(μ~3-NH)(μ~2-NO) (μ~2-CO)Fe_2(CO)_6(M=Mo,III:M=W,IV),based on the reaction of (η~5-C5_H_4)M(CO)_3Cl with Na[Fe(CO)_3NO] at room tem-perature,have been demonstrated,The crystal structures of II and IV arealso presented.     

金属簇合物η~5-RC_5H_4(CO)_2MCo_3(CO)_6(μ-CO)_3的合成、结构及反应机理的研究

通过金属单键化合物[η~5-RC_5H_4(CO)_3M]_2和CO_2(CO)_8的热反应,制得8个含烷基环戊二烯基配体的金属四面体簇合物η~5-RC_5H_4(CO)_2MCo_3(CO)_6(μ-CO)3(M=Mo,W;R=CH_3,C_2H_5,n-C_4H_9,C_6H_5CH_2)。除用元素分析,IR,~1H NMR和MS表征了它们的结构以及用X光衍射技术测得η~5-n-C_4H_9C_5H_4(CO)_2MoCo_3(CO)_6(μ-CO)_3的单晶分子结构外,尚对该反应的机理进行了研究。所测晶体属空间群P2_1/c,晶胞参数a=10.088 (2),b=13.063 (3),c=18.320 (5) A;β=96.04 (2)°,最终偏差因子R=0.041。     

Synthesis and CrystaI Structure of(η5-EtO(O)CC5H4)RuCoMo(μ3-S)(CO)8

The chiral sulfido cluster (η5-EtO(O)CC5H4)RuCoMo(μ3-S)(CO)8 was synthesized by refluxing a solution of SRuCo2 (CO)9 and Na[Mo(CO)3CpC(O) OEt] in tetrahydrofuran. It was characterized by elemental analysis, IR and 1H-NMR.Crystal data: C 16H9O)10CoMoRuS, Mr=649.24, monoclinic, space group P21/n, a =10.075(1), b = 9.034(2), c = 22.973(7) A, β= 92.70(1), V = 2088.7(8)A3,296K, final R = 0. 030, Rw= 0. 042 for 3686 observed reflections with I＞2. 00σ(I).The crystal structure determination shows that the cluster has a chiral tetrahedral core containing a ethoxycarbonyl attached to the cyclopentadienyl.     

Synthesis,characterization and crystal structures of heterometallic trinuclear carbonyl sulfido clusters (η5-Cp)MoFeCo- (CO)8(μ3-S) and [(η5-Cp)Mo]2Fe(CO)7(μ3-S)

HFe2Co(CO)9(3-S) reacts with (5-Cp)Mo(CO)3Cl in refluxing THF to give heterometallic trinuclear clusters (5-Cp)MoFeCo(CO)8(3-S) and [(5-Cp)Mo]2Fe(CO)7-(3-S), which have been characterized by elemental analyses, i.r., 1H- and 13C-n.m.r. and X-ray crystal structure determination. An electrophilic addition–elimination sequence is proposed for their formation.     

New triosmium–iridium clusters: Synthesis and molecular structure of [Os3Ir2(Cp1)2(μ-OH)(μ-CO)2(CO)8Cl] (1), [Os3IrCp1(μ-OH)(CO)10Cl] (2), [Os3IrCp1(μ-H)(μ-Cl)(η3,μ3-C5H2N(NH2)Br)(CO)9] (3) and [Os3IrCp1(μ-Cl)2(η2,μ3-C5H3N(NH)Br)(CO)7] (4)

The trinuclear osmium carbonyl cluster, [Os₃(CO)₁₀(MeCN)₂], is allowed to react with 1 equiv. of [IrCp¹Cl₂]₂ (Cp¹ = pentamethylcyclopentadiene) in refluxing dichloromethane to give two new osmium–iridium mixed-metal clusters, [Os₃Ir₂(Cp¹)₂(μ-OH)(μ-CO)₂(CO)₈Cl] (1) and [Os₃IrCp¹(μ-OH)(CO)₁₀Cl] (2), in moderate yields. In the presence of a pyridyl ligand, [C₅H₃N(NH₂)Br], however, the products isolated are different. Two osmium–iridium clusters with different coordination modes of the pyridyl ligand are afforded, [Os₃IrCp¹(μ-H)(μ-Cl)(η³,μ₃-C₅H₂N(NH₂)Br)(CO)₉] (3) and [Os₃IrCp¹(μ-Cl)₂ (η²,μ₃-C₅H₃N(NH)Br)(CO)₇] (4). All of the new compounds are characterized by conventional spectroscopic methods, and their structures are determined by single-crystal X-ray diffraction analysis.     

Synthesis and structures of bridged diruthenium complexes (E)[η5-C5H4)Ru(CO)]2(μ-CO)2 (E = Me2Ge,Me2SiOSiMe2, Me2SiOSiMe2OSiMe2)

A series of bridged diruthenium complexes (E)[(⁵-C₅H₄)Ru(CO)]₂(-CO)₂ (E = Me₂Ge (2); Me₂SiOSiMe₂ (3); Me₂SiOSiMe₂OSiMe₂ (4)) has been prepared by reacting Ru₃(CO)₁₂ with Cp₂E in refluxing heptane. The molecular structures of (2) and (4) have been determined by X-ray diffraction.     

Co3(CO)7(μ3-S)(μ,η2-SCNR2)的合成和晶体结构

Co2(CO)8与4个二硫代双(烷基硫代甲酰胺)类前配体[R2NC(S)S]2反应,得4个含烷基硫代甲酰胺基的三核钴羰基硫簇合物.通过元素分析、IR、1H NMR和MS等方法表征了它们的结构,用X射线衍射法测定了其中一个簇合物Co3(CO)7(μ3-S)[μ,η2-SCN(i-Pr)2](Ⅲ)的晶体结构.晶体属单斜晶系,P21/n空间群,晶胞参数a=1.145 2(2)nm,b=1.502 8(3)nm,c=1.2144(2)nm,a=90°,β=92.15(3)°,γ=90°,V=2.088 5(7)nm3,Z=4,F(000)=1 096,Dc=1.747 mg·m-3,GOF(F2)=0.835,μ=2.588 nm-1.最终因子R[I＞2σ(I)]=0.040 7,Rw=0.062 4.     

钼铁混合金属原子簇的研究Ⅱ(η~5-C_5H_5)_2M_(o2)F_(e2)(μ_3-T_e)_2(μ_3-CO)-(μ_2-CO)(CO)_5的合成及结构

钼铁混合金属原子簇Mo_2Fe_2Te_2(CO)_7(η~5-C_5H_5)_2是Fe_3Te_2(CO)_9与Mo_2(CO)_6(η~5～C_5H_5)_2反应所得的产物之一。它的晶体属正交晶系,空间群为Pbn2_1。晶胞参数:a=12.172(5);b=13.595(2);c=12.924(4)A,V=2138.5(2)A~3。晶体结构由直接法及差值Fourier合成解出,经最小二乘法修正,最终R因子为0.030(3233个Ⅰ>26(Ⅰ)的反射)。在簇分子中,四个金属原子呈四面体构型,两个μ_8-Te原子和一个不对称的μ_8-CO分别桥连到四面体的三个三角面的金属原子上,从而构成了缺顶点的类立方烷结构。     

Synthesis of Platinum-Triruthenium Clusters Using the Zero-Valent Platinum Reagent Pt(nb)3: X-Ray Crystal Structures of Ru3Pt(CO)11(P-iPr3)2, Ru3Pt(μ-H)(μ3-η3-MeCCHCMe)(CO)9(P-iPr3), Ru3Pt(μ3-η2-PhCCPh)(CO)10(P-iPr3), Ru3Pt(μ-H)(μ4-N)(CO)10(P-iPr3) and Ru3Pt(μ-H)(μ4-η2-NO)(CO)10(P-iPr3)

The complexes Pt(nb)_3-n(P-iPr₃)_n (n=1, 2, nb=bicyclo[2.2.1]hept-2-ene), prepared in situ from Pt(nb)₃, are useful reagents for addition of Pt(P-iPr₃)_n fragments to saturated triruthenium clusters. The complexes Ru₃Pt(CO)₁₁(P-iPr₃)₂ (1), Ru₃Pt(-H)(₃-³-MeCCHCMe)(CO)₉(P-iPr₃) (2), Ru₃Pt(₃-²-PhCCPh)(CO)₁₀(P-iPr₃) (3), Ru₃Pt(-H)(₄-N)(CO)₁₀(P-iPr₃) (4) and Ru₃Pt(-H)(₄-²-NO)(CO)₁₀(P-iPr₃) (5) have been prepared in this fashion. All complexes have been characterized spectroscopically and by single crystal X-ray determinations. Clusters 1–3 all have 60 cluster valence electrons (CVE) but exhibit differing metal skeletal geometries. Cluster 1 exhibits a planar-rhomboidal metal skeleton with 5 metal–metal bonds and with minor disorder in the metal atoms. Cluster 2 has a distorted tetrahedral metal arrangement, while cluster 3 has a butterfly framework (butterfly angle=118.93(2)°). Clusters 4 and 5 posseses 62 CVE and spiked triangular metal frameworks. Cluster 4 contains a ₄-nitrido ligand, while cluster 5 has a highly unusual ₄-²-nitrosyl ligand with a very long nitrosyl N–O distance of 1.366(5) Å.