Synthesis and X-ray crystal structure of the electron-deficient metal carbonyl cluster [Os3(CO)5(μ3-H)(μ-H)(μ-PtBu2)2(μ-Ph2PCH2PPh2)]

The reaction of [Os₃(CO)₁₀(μ-dppm)] (1) with ^tBu₂PH in refluxing diglyme results in the electron-deficient metal cluster complex [Os₃(CO)₅(μ₃-H)(μ-P^tBu₂)₂(μ-dppm)] (2) (dppm = Ph₂PCH₂PPh₂) in good yields. The molecular structure of 2 has been established by a single crystal X-ray structure analysis. In contrast to the known homologue [Ru₃(μ-CO)(CO)₄(μ₃-H)(μ-H)(μ-P^tBu₂)₂(μ-dppm)] (3), no bridging carbonyl ligand was found in 2. The electronically unsaturated cluster 2 does not react with carbon monoxide under elevated pressure, therefore 2 seems to be coordinatively saturated by reason of the high steric demands of the phosphido ligands.     

A New Preparation of Mo2(CO)8(μ-PPh2)2 and W2(CO)8(μ-PPh2)2 by a Phosphorus-Carbon Bond Cleavage Reaction. Crystal Structure of a New Polymorph of Mo2(CO)8(μ-PPh2)2

A new synthesis of Mo₂(CO)₈(-PPh₂)₂ and W₂(CO)₈(-PPh₂)₂ by the reaction of molybdenum and tungsten hexacarbonyls with a tetraazamacrocyclic ligand containing —CH₂PPh₂ side chains, comprising cleavage of the phosphorus-methylene bond has been performed. The complexes have been investigated by magnetic and spectroscopic measurements and by single-crystal structure analyses. The structural characterization of a new polymorph of Mo₂(CO)₈(-PPh₂)₂ has been described.     

A hexanuclear cobalt(III) complex containing the pseudocubane fragment [Co4(μ4-O)2(μ3-O)2] in its metal framework and a solvated dibenzyl ether molecule

Room-temperature oxidation of a mixture of the complex (Co^II)₃(μ-OOCBu _t )₆(NEt₃)₂ and dibenzyl ether (DBE) with atmospheric oxygen in dichloromethane-benzene (4: 1) gave the hexanuclear complex [(Co^III)₆(μ₄-O)₂(μ₃-O)₂(μ-OOCBu ^t )₉(OH)₂(HOOCBu ^t )](HNEt₃) · 0.5DBE · C₆H₆ (I) as the major reaction product. According to X-ray diffraction data, the metal framework of complex I contains the pseudocubane fragment [Co₄(μ₄-O)₂(μ₃-O)₂] linked with two “peripheral” cobalt(III) ions. The possibility of using complex I as an intermediate catalyst for liquid-phase oxidation of DBE as well as the conformational changes in the DBE molecule due to its adaptation to the metal complexes are discussed.     

Synthesis, Structure and Properties of a Copper Complex Cu2(μ-PhCOO)2(μ-CH3COO)2(CH3OH)2

The title complex Cu2(μ-PhCOO)2(μ-CH3COO)2(CH3OH)2 1(C20H24Cu2O10, Mr=structure was determined by X-ray diffraction method. Complex 1 belongs to orthorhombic, space group Pbca with a = 13.083(6), b = 8.078(4), c = 21.566(2)(A), V = 2279(2) (A)3, Z = 4, Dc= 1.607g/cm3, F(000) = 1128,μ(MoKa) = 1.918 mm-1, the final R = 0.0506 and wR = 0.1382. Each Cu(Ⅱ)ion is coordinated by five oxygen atoms from two benzoic acids, two acetic acids and one methanol molecule in a slightly distorted square pyramidal environment. The title molecules construct a 2-D complex 1 displays strong emissions. IR and TG-DTA studies are also presented.     

Synthesis and Structure of a Novel Mg6 Cluster Molecule Mg6(μ3-OH)2(μ3-Br)2(μ-Br)8(THF)8

A novel Mg₆ cluster molecule with the formula of Mg₆( ₃-OH)₂( ₃-Br)₂(-Br)₈(THF)₈ (1) has been isolated in 38% yield from a reaction of the Grignard reagent, 2-naphthyl-Mg-Br with BBr₃ in THF. The structure of 1, determined by a single-crystal X-ray diffraction analysis, contains two Mg₃ triangles linked together by two bridging bromide ligands. Within each Mg₃ triangle, one hydroxide and one bromide ligand function as triply bridging ligands capping both sides of the Mg₃ triangle. The coordination geometry around each Mg(II) ion is approximately octahedral. NMR studies revealed that compound 1 is highly fluxional in solution.     

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 structure of a novel bis-μ-oxo rhenium(VI) dimer: Re2O2(μ-O)2(CH2CMe2Ph)4

The complex Re(O)Cl₃(PPh₃)₂ reacts with dialkyl zinc reagents in CH₂Cl₂ to give the novel bis-μ-oxo rhenium(VI) dimer [Re(O)(μ-O)R₂]₂. The molecular structure has been determined by single-crystal X-ray diffraction methods.     

A double-bonded niobium(III) compound with a formamidinate core: Nb2(μ-SMe)2(μ-DTolF)2 (η2-DTolF)2.2 toluene,DToIF= di-p-tolylformamidinate

The reaction of NaEt₃BH with Nb₂(-SMe₂)₃Cl₆ results in the transfer of a hydride ion to dimethylthioether with concomitant production of methane. Further reaction with potassium di-p-tolylformamidinate, KDTolF, yields Nb₂(-SMe)₂(-DTolF)₂²-DTolF:)₂.2 toluene, 1. In the latter, two thiomethoxide ions and two DTolF groups bridge the trivalent niobium atoms. Each of the other two DTolF groups chelate a metal atom to give the molecule an edge-sharing bioctahedral structure, The niobium-niobium distance of 2.655(2) A is consistent with the presence of a double bond between the metal atoms.     

Synthesis,Characterization and Molecular Structure of a Diiron Complex(μ-SCH_2CH_2CH_2S-μ)Fe_2(CO)_5(Ph_2PCH_3)

The title complex,(μ-pdt)Fe_2(CO)_5(Ph_2PCH_3)(pdt = SCH_2CH_2CH_2S),was obtained by the reaction of the parent complex(μ-pdt)Fe_2(CO)_6 with Ph_2PCH_3 and Me_3NO·2H_2O in good yield(90%). The title complex was characterized by IR,~1H NMR,~(31)P{~1H} NMR and ~(13)C{~1H} NMR spectroscopy as well as by single-crystal X-ray diffraction analysis. The molecular structure shows that the title complex contains a butterfly diiron propanedithiolate cluster with five terminal carbonyls and a monophosphine ligand Ph_2PCH_3. The crystal packing diagram reveals that intermolecular C H···O hydrogen bonds between CH_2 and carbonyls,π-π stacking interactions and van der Waals' interactions stabilize the solid state to form a three-dimensional network.     

Synthesis and structural characterization of [Au2Pd14(μ3-CO)7(μ2-CO)2(PMe3)11](PF6)2—An icosahedrally-based high nuclearity mixed metal cluster

[Au₂Pd₁₄(₃-CO)₇(₂-CO)₂(PMe₃)₁₁](PF₆)₂ has been synthesized from [Pd₈(CO)₈(PMe₃)₇] and AuCl(PCy₃) in the presence of TIPF₆. It has been characterised on the basis of mass spectrometry, infrared and NMR spectroscopy, and a single crystal X-ray diffraction study. The structure is based on a palladium-centered Au₂Pd₁₁ icosahedron which shares an edge with a Pd₅ trigonal bipyramid.This paper is dedicated to Larry Dahl on his 65th Birthday—his enthusiasm and achievements in cluster chemistry have inspired us all for more than 30 years.     

Dinuclear Ruthenium(II) Carbonyl Complexes Doubly Bridged by a Bromine Atom and a C5H3N-2-C(O)CH2-6-CH2 (Q) Group. Crystal Structures of Ru2(μ-Br)(μ-Q)Br(CO)4(PPh3)(MeOH) and Ru2(μ-Br)(μ-Q)Br(CO)3(PPh3)2

The oxidative addition reaction of 2,6-bis(bromomethyl)pyridine to Ru₃(CO)₁₂ gave scarcely soluble {Ru₂Br₂(-Q)(CO)₄} _n , 1, [Q=C₅H₃N-2-C(O)CH₂-6-CH₂] or a mixture of 1 and the mononuclear complex RuBr(Q)(CO)₃, 2, [Q=C₅H₃N-2-C(O)CH₂-6-CH₂Br] according to the reactant's mole ratio. Further reactions of 1 with some N- and P-donor ligands (L) afforded readily soluble dinuclear complexes, Ru₂(-Br)(-Q)Br(CO) _n (L) _m [n=4, m=1, L=PPh₃ 3a, or py 3b; n=3, m=2, L=PPh₃ 5a, or PPh₂(o-tolyl) 5b]. In this paper, the characterization of these products by the elemental analyses and the spectroscopic methods are described. The X-ray crystal structures of Ru₂(-Br) (-Q)Br(CO)₄(PPh₃)(MeOH), 4, which was obtained by crystallization of 3a from MeOH, and of 5a · (2CHCl ₃ ) are also described. Each of the metal atoms in 4 has a distorted octahedral coordination, while in 5a · (2CHCl ₃ ) one metal atom takes a distorted octahedral geometry and the other pseudooctahedral, which is completed by presenting a Ru ··· Br secondary bonding interaction.     

CRYSTAL AND MOLECULAR STRUCTURE OF (μ-SPh) (μ-SCH2CH2CN)Fe_2 (CO)_6

<正> The crystal and molecular structure of (μ-SPh)(μ-SCH2CH2CN)Fe2-(CO)5 has been determined by X-ray diffraction method. The crystals of this complex are triclinic, space group P1,with a=ll.175(1), b=ll.877(2), c= 15.640(2)1,α=106.20(1),β=103.15(1),γ=98.46(1)°; Z=4; Dc=1.67g/cm3. The final structure refinement converged with unweighted and weighted R factors of 0.028 and 0.034 for 2853 observed unique reflections.     

Co-ordinatively unsaturated metal cluster compounds: Facile reactivity of the phosphinidene-capped phosphido-bridged triruthenium cluster [Ru3(μ3-PPh)(μ2-PPh2)2(CO)7]

The purple, phosphinidene-capped, phosphido-bridged triruthenium cluster [Ru₃(μ₃-PPh)(μ₂-PPh₂)₂(CO)₇] reacts readily with carbon monoxide, trimethylphosphite, sodium borohydride and diphenylacetylene under mild conditions to afford product mixtures from which [Ru₃(μ-PPh)(μ₂-PPh₂)₂(CO)_7+n] (n = 1, 2 or 3), [Ru₃(μ₃-PPh)(μ₂-PPh₂)₂(CO)₆{P(OMe)₃}], [Ru₃(μ₃-η³-PhPCPhCPh)(μ₂-PPh₂)₂(CO)₆], respectively, can be isolated. The structure of [Ru₃(μ₃-PPh)(μ₂-PPh₂)₂(CO)₆{P(OMe)₃}] has been established X-ray crystallographically.     

Properties of a New 58-Electron Butterfly [Pt4(μ2-dpam)3(μ2-CO)3(η1-dpam)]2+ Cluster

A new organometallic cluster [Pt₄(₂-dpam)₃(₂-CO)₃(¹-dpam)] X₂ (X=CF₃CO ₂ ^- ; 4a) was prepared from a reaction between Pt(dpam)(CF₃CO₂)₂ and CO in a methanol (water mixture). The PF ₆ ^- salt 4b is obtained from an anion exchange with NH₄PF₆ in methanol. Dark red crystals suitable for X-ray crystallography (X=PF ₆ ^- ) revealed the commonly encountered butterfly structure for a 58-electron Pt cluster (angle between the two Pt₃ planes =95.36(8)°, nonbonding Pt...Pt distance =3.094(1) Å). The structure consists of two edge sharing Pt₃ triangles, a small one 'Pt₃(₂-dpam) ₃ ²⁺ and a larger one Pt₃(₂-CO)₃(L)₃ where L=As group. The Extended Huckel Molecular Orbital calculations (EHMO) have been rationalized from interactions of two L and PtL ₂ ²⁺ fragments onto the planar triangular Pt₃(₂-CO)₃L₃ cluster (L = AsH₃). The compound is luminescent at 77 K with a structureless band located at 690 nm (_e=3.2 ±0.2s). Finally, the ¹H NMR spectra are interpreted, particularly with respect to fluxionality and presence of two isomers. X-ray data for 4b: orthorhombic, C c2a, a=26.320(9), b=27.613(6), c=28.891(4) Å, V=20998(9) ų, Z=4, D(calc.)=1.925 Mg/m³.     

Synthesis and characterisation of hexanuclear ruthenium clusters containing a μ4-nitrene ligand. Crystal structures of [Ru6(CO)15(μ-CO)2(μ4NH)(μ-OMe)μ3-η2-N(H)C(O)OMe] and [Ru6(CO)16(μ-CO)2(μ4-NH)(μ-OMe)(μ-NCO)]

Two hexaruthenium carbonyl clusters [Ru₆(CO)₁₅(μ-CO)₂(μ₄-NH) (μ-OMe){μ₃-η²-N(H)C(O)OMe}] and [Ru₆(CO)₁₆(μ-CO)₂-(μ₄-NH)(μ-OMe)(μ-NCO)]2 have been isolated from the pyrolysis of H₂Ru₃(CO))₉NOCH₃, and single-crystal X-ray structure analysis shows that both 1 and 2 have a square planar arrangement of four ruthenium atoms capped by a μ₄-nitrene ligand, with two additional ruthenium atoms bridging two opposite RuRu edges of the square base to form a ‘boat’ form metal framework.     

(μ-RS)(μ-XMgS)Fe2(CO)6亲核性能的研究:铁硫配合物(μ-RS)[μ-Cp(CO)2FeS]Fe2(CO)6

研究了(μ-RS)(μ-XMgS)Fe2(CO)6与π-环戊二烯二羰基碘化铁的反应.首次制得(μ-RS)[(μ-CpFe(CO)2S]Fe2(CO)6的一系列含有机铁硫桥的非对称配合物.它们的核磁氢谱表明每个络合物只是以一类构象体存在.它们的甲基络合物的单晶结构分析证实了这一结论.     

双簇核铁硫配合物[(μ-RS)Fe2(CO)6]2(μ-S-S-μ)的合成

本文报导由μ-S2F2(CO)6及格氏试剂形成的活泼配合物(1), 可在磺酰氯SO2Cl2的作用下, 发生氧化偶联反应生成由S-S键相连的双簇核配合物(2), 本文对所得配合物(2)的反应性能进行了研究。