Reactions of neodymium(ii), dysprosium(ii), and thulium(ii) diiodides with cyclopentadiene. Molecular structures of complexes CpTmI2(THF)3 and [NdI2(THF)5]+[NdI4(THF)2]–

The reactions of LnI₂ (Ln = Nd (1) or Dy (2)) with cyclopentadiene (CpH) in THF at 0 °C afforded the CpLnI₂(THF)₃ complexes in 65—67% yields. The reaction of thulium diiodide (3) with an excess of CpH at 60 °C produced CpTmI₂(THF)₃, Cp₂TmI(THF)₂, and TmI₃(THF)₃ in 21, 58, and 63% yields, respectively. The reactions of 1 and 2 with pentamethylcyclopentadiene (Cp*H) in THF were accompanied by disproportionation giving rise to the Cp*₂LnI(THF)₂ and LnI₃(THF) _x complexes. Neodymium triiodide was isolated in the ionic form [NdI₂(THF)₅]⁺[NdI₄(THF)₂]^–. Its structure and the structure of CpTmI₂(THF)₃ were established by X-ray diffraction analysis.     

Reduction of nitrogen with neodymium(II) and dysprosium(II) diiodides and selected properties of the resulting nitrides

The diiodides NdI₂ and DyI₂ react with nitrogen at an atmospheric pressure at 2704-550 °C to give the nitrides (LnI₂)₃N (Ln = Nd and Dy). The products obtained are insoluble in organic solvents; in THF, they rapidly disproportionate into LnI₃(THF)₃ and the iodide nitrides (NdI)₃N₂ of unclear structures. The nitrides (NdI₂)₃N and (DyI₂)₃N can be completely hydrolyzed into ammonia, the triiodide hydrates LnI₃(H₂O)₂, and the monoiodide hydrates LnI(OH)₂(H₂O). A reaction of (NdI₂)₃N with excess iodobenzene in THF gives Ph₃N and PhNH₂ in 9 and 5% yields, respectively. Reactions of (NdI₂)₃N with propyl chloride, benzyl chloride, and acetyl chloride produce no nitrogen-containing products. A reaction of (NdI₂)₃N with CpK gives Cp₃Nd(THF) in 63% yield.     

Synthesis and some properties of neodymium(<Emphasis Type="SmallCaps">III</Emphasis>) and dysprosium(<Emphasis Type="SmallCaps">III</Emphasis>) iodide hydrides LnI<Subscript>2</Subscript>H

The iodide hydrides NdI₂H (1) and DyI₂H (2) were obtained by the reactions of diiodides NdI₂ (3) and DyI₂ (4) with hydrogen at atmospheric pressure and temperature of 120–200 °C. Hydrolysis of products 1 and 2 gives hydrogen in a high yield. The reactions of 1 with phenol and of 2 with isopropyl alcohol in THF afford the iodide phenoxide NdI₂(OPh)(THF)₄ and iodide isopropoxide DyI₂(OPrⁱ)(PrⁱOH)₃, respectively. The reaction of 2 with cyclopentadiene is accompanied by disproportionation and gives, besides dihydrogen, Cp₂DyI(THF)₂ and DyI₃(THF)₃. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1887–1889, October, 2007.     

Chemiluminescence in the reaction of LnI<Subscript>2</Subscript> (Ln = Dy,Nd) with water

Chemiluminescence (CL) upon the reaction of crystalline LnI₂ (Ln = Dy, Nd) with water was found. The CL emitters are the Ln³⁺* electron-excited ions (Dy³⁺*, λ_max = 470, 570 nm; Nd³⁺*, λ = 700–1200 nm) generated by the electron transfer from the Ln^II ions to the H₂O molecules. The identified reaction products are H₂, dissolved LnI₃, and insoluble LnI(OH)₂ (49–51% and 48–50% yield for DyI₂ and NdI₂, respectively). The treatment of NdI₂ with an H₂O solution in THF gives the NdI₂OH(thf)₂·3H₂O complex and hydrogen. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1890–1893, October, 2007.     

On the Reactivity and Stability of Iodide–Nitride–Sulfide Clusters of Neodymium and Dysprosium

The thermal decomposition of cluster Nd₃I₅(S₂)(S₂N₂)(THF)10 (I) at 50–400°C affords a mixture of products among which tetrahydrofuran (THF), sulfur, diiodine, HI, H₂S, CS₂, S₃N₆, S₃N₅, MeI, thiophene, tetrahydrothiophene, diiodobutane, iodobutene, and NdI₃ are identified. The treatment of Ln₃I₅(S₂)(S₂N₂)(THF)₁₀ (Ln = Nd (I), Dy (II)) with phenanthroline (Phen) in THF at room temperature results in the partial substitution of ТНF to form new complexes Ln₃I₅(S₂)(S₂N₂)(THF)₄(Phen)₃. The dissolution of compound I in pyridine gives a pyridine (Py) complex Ln₃I₅(S₂)(S₂N₂)(THF)3(Py)₇. The dissolution of compounds I and II in acetonitrile at 20°C is accompanied by the fast rearrangement and fragmentation of the complexes to form LnI₃(MeCN)₆, [LnI(S₂)(MeCN)], and [LnI(S₂N₂)(MeCN)]. Complex I in THF does not react with white phosphorus, carbon monoxide, fullerene C₆₀, and chromium hexacarbonyl.     

Neodymium and dysprosium diiodides in the synthesis of vanadocene and cobaltocene

The reaction of NdI₂ or DyI₂ with VCl₃ and cyclopentadiene in THF at 65–70 °C without isolation of the intermediates afforded vanadocene in 55 and 68% yields, respectively. An analogous reaction of DyI₂ with CoCl₂ at 50 °C produced Cp₂Co in 38% yield.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2086–2088, October, 2004.     

Reaction of neodymium diiodide with methanol in acetonitrile. Structure of the cluster [Nd4(μ2-I)1.1(μ3-I)(μ2-OMe)4.9(μ4-O)(MeCN)12]I3

The reaction of neodymium diiodide NdI₂ with excess methanol in acetonitrile produced the tetranuclear neodymium cluster [Nd₄(μ₂-I)_1.1(μ₃-I)(μ₂-OMe)_4.9(μ₄-O)(MeCN)₁₂]I₃ (1). In the latter, the isomorphic substitution of one methoxy group by an I⁻ anion with site occupancies (%) of 90 and 10, respectively, was observed. Due to the isomorphic substitution in the crystal, cluster 1 can be considered as a superposition of two complexes, [Nd₄(μ₂-I)(μ₃-I)(μ₂-OMe)₅(μ₄-O)(MeCN)₁₂]I₃ and [Nd₄(μ₂-I)₂(μ₃-I)(μ₂-OMe)₄(μ₄-O)(MeCN)₁₂]I₃. The characteristic feature of cluster 1 is that the center of the Nd₄ cage is occupied by the μ₄-coordinated O²⁻ anion, which is indicative of the partial O-C bond cleavage in methanol. The reaction of NdI₂ with an equimolar amount of MeOH in an acetonitrile solution produced methoxide NdI₂(OMe)(MeCN)₄ in 49% yield. Dedicated to Professor W. J. Evans on the occasion of his 60th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1894–1897, October, 2007.     

Complexes of neodymium and dysprosium triiodides with amines. Molecular structures of the {Dy[Me2N(CH2)3NH2]8}I3, NdI3(PriNH2)4, and NdI3(PriNH2)5 complexes

The dissolution of DyI₂ in diamine Me₂N(CH₂)₃NH₂ (DMDA) is accompanied by the disproportionation of the salt, hydrogen evolution, and oxidation of Dy^II to Dy^III. The [Dy(DMDA)₈]I₃ complex (1) was isolated from the solution. The neodymium amide amine complex (PrⁱNH)NdI₂(IPA)₄ was produced by the reaction of NdI₂ with isopropylamine (IPA). The recrystallization of this complex from IPA afforded the NdI₃(IPA)₄ complex (2). The recrystallization of (PrⁱNH)NdI₂(IPA)₄ from a toluene-IPA mixture gave the complex with five amine ligands, NdI₃(IPA)₅ (3). The structures of compounds 1, 2, and 3 were established by X-ray diffraction. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1674–1679, September, 2007.     

A structural variability of copper(I) chloride-tetrahydrothiophene adducts crystallizing in polymeric forms and exhibiting polymorphism: The role of the solvent

The function of the solvent in the self-assembling mode of [CuCl] with tetrahydrothiophene is reported. Copper(l) chloride has been used in the form of [CuCOCl] _n , which is slightly soluble in the most common solvents, and to allow an homogeneous phase reaction. The reaction of [CuCOCl] _n with THT gave [(CuCl)₂(THT)₃] _x ,1, in CH₃OH, [(CuCl)(THT)₂] _x ,2 in THF [(CuCl)(THT)] _x ,3, in CH₂Cl₂, and [(CuCl)₃(THT)₂] _x ,4, in DME. Compound1 consists of polymeric chains of centrosymmetric Cu₂Cl₂ dinuclear units bridged by THIT molecules running parallel to the [101] axis. In the structure of2 we found polymeric layers generated from the [(CuCl)(THT)] asymmetric unit by the center of symmetry and by the twofold axis. In compound3 the structure consists of layers generated through the center of symmetry by the [(Cu₂Cl₂)(THT)₂] asymmetric unit, while4 consists of layers generated through the center of symmetry by the [(Cu₃Cl₃)(THT)₂] asymmetric unit. Crystallographic details are as [ollows:2 is monoclinic, space group P2₁/c.a=9.657(3) A,b=6.441(2) A,c=11.459(3) A,\=111.96(2)°,V=661.0(4) A³. andR=0.075;3 is monoclinic, space group P2₁/n,a=19.327(7) A,b=6.703(2) A,c=10.116(3) A,ß=103.04(3)°,V=1276.7(7) A³ andR=0.043:4 is triclinic, space group Pl,a=12.513(2) A,b=6.698(1) A,c=9.651(1) A,=91.98(1)°,\=107.86(1)°,=74.59(1)°,V=741.2(2) A³, andR=0.044.     

Reactions of benzonitrile with diiodides of neodymium, dysprosium, and thulium

The reactions of LnI₂ (Ln = Nd, Dy, Tm) with benzonitrile are accompanied by disproportionation, resulting in the formation of triiodides LnI₃(PhCN)₄ and an intractable mixture of monoiodine derivatives LnI(R)R". Hydrolysis of the mixture gives 2,4,6-triphenyl-1,3,5-tiazine, 2,3,5,6-thetraphenyl-1,4-pyrazine, and 2,4,5-triphenylimidazole. The reaction of dysprosium diiodide with acrylonitrile gives a metal-containing polymer with a molecular weight of 2700. Treatment of the polymer with water results in separation of DyI₂(OH)(H₂O) _x to give metal-free polyacrylonitrile with a molecular weight of 2400.     

Synthesis, Structure, and 31P NMR of Sulfur/Oxygen-Bridged Incomplete Cubane-Type Molybdenum and Tungsten Clusters with Triphenylphosphine Ligands

Sulfur/oxygen-bridged incomplete cubane-type triphenylphosphine molybdenum and tungsten-clusters [Mo₃S₄Cl₄(H₂O)₂(PPh₃)₃]·3THF (1A), [Mo₃S₄Cl₄(H₂O)₂(PPh₃)₃]·2THF (2A), [Mo₃OS₃Cl₄(H₂O)₂(PPh₃)₃]·2THF (1B), and [W₃S₄Cl₄(H₂O)₂(PPh₃)₃]·2THF (1C) were prepared from the corresponding aqua clusters and PPh₃ in THF/MeOH. On recrystallization from THF, procedures with and without addition of hexane to the solution gave 1A and 2A, respectively, while the procedures gave no effect on the formation of 1B and 1C. Crystallographic results obtained are as follows: 1A: monoclinic, P2₁/n, a=17.141(4) Å, b=22.579(5) Å, c=19.069(4) Å, =96.18(2)°, V=7337(3) ų, Z=4, R(R _w)=0.078(0.102); 1C: monoclinic, P2 ₁/c, a=12.635(1) Å, b=20.216(4) Å, c=27.815(3) Å, =96.16(1)°, V=7062(2) ų, Z=4, R(R _w)=0.071(0.083). If the phenyl groups are ignored, the molecule [Mo₃S₄Cl₄(H₂O)₂(PPh₃)₃] in 2A has idealized CS symmetry with the mirror plane perpendicular to the plane determined by the metal atoms, while the molecule in 1A does not have the symmetry. The tungsten compound 1C is isomorphous with the molybdenum compound 2A. ³¹P NMR spectra of 1A, 2A, and 1C were obtained and compared with similar clusters with dmpe (1,2-bis(dimethylphosphino)ethane) ligands.     

Synthesis and characterization of the new mixed-metal,mixed-chalcogen clusters Fe2 M(CO)10(μ3-S)(μ3-Te) (M=W,Mo). crystal structure of Fe2W(CO)10(μ3-S)(μ3-Te)

The new clusters Fe₂ M(CO)₁₀(µ₃-S)(µ₃-Te), I (M=W) and 2 (M=Mo) have been isolated from the room temperature reaction of Fe₂(CO)₆(µ-STe) andM(CO)₅(THF) (M=W, Mo), respectively. Compounds1 and2 have been characterized by IR, 125 Te NMR spectroscopy, and elemental analysis. The structure of compound1 has been established by X-ray crystallography. It belongs to the triclinic space groupP witha=6.844(2) Å,b=9.397(2) Å,c=13.681(10) Å, =81.64(2)°,=81360r,=812(2)°,V=861.2(3) ų,Z=2,D _e =2.835 g cm^–3. Full-matrix least-squares refinement of1 converged to R=0.043, andR _w .=0.115. The structure consists of a Fe₂ WSTe square pyramid and the W atom occupies the apical site of the square pyramid.     

Heterometallic Alkoxide Complexes of Variable Composition—A New Way to Ultrafine Powders of Metal Alloys

The anodic oxidation of Re metal in MeOH (Me = CH₃) provides a mixture of Re₂O₃(OMe)₆ and Re(V) oxoalkoxides that on storage or on heating give insoluble and air stable Re₄O_6–y (OMe)_12+y (I). I can be also obtained by reaction of Re₂O₇ with MeOH. In the presence of MoO(OMe)₄, a heterometallic complex ReMoO₂(OMe)₇(II) is formed as intermediate, the final product being Re_4–x Mo _x O_6–y (OMe)_12+y (III). The electrosynthesis in the presence of WO(OMe)₄ gives Re_4–x W _x O_6–y (OMe)_12+y (IV) only at very high Re : W ratios in solutions and the W content varies in one and the same sample. The dissolution of Re₂O₇ in the solutions of MO(OMe)₄, M = Mo,W in toluen on reflux yields Re_4–x M _x O_6–y (OMe)_12+y with uniform Re : M distribution. The cocrystallization of MoO(OMe)₄ and WO(OMe)₄ yields (Mo,W)O(OMe)₄ (V) with almost uniform Mo : W distribution. The thermal decomposition of II and III in inert atmosphere gives fine powder of the (Re,Mo)O₂ phase. The reduction with hydrogen gas converts II and III into an ultrafine powder of Re–Mo alloy at temperatures below 400°C. The latter can be sintered into compact metal at 800–900°C.     

Facile generation of platinum(IV) compounds with mixed labile moieties. Hydrogen peroxide oxidation of platinum(II) to platinum(IV) compounds

Hydrogen peroxide oxidation of platinum(II) compounds containing labile groups such as Cl, OH, and alkene moieties has been carried out and the products characterized. The reactions of [Pt^II (X)₂ (N–N)] (X = Cl, OH, X₂ = isopropylidenemalorate (ipm); N–N 2,2-dimethyl-1,3-propanediamine [(dmpda), N-isopropyl-1,3-propanediamine (ippda)] with hydrogen peroxide in an appropriate solvent at room temperature affords [Pt^IV (OH)(Y)(X)₂(N–N)] (Y = OH, OCH₃). The crystal structures of [Pt^IV(OH)(OCH₃)(Cl)₂(dmpda)]·2H₂O (P-1 bar, a = 6.339(2) Å , b = 9.861(1) Å, c = 11.561(1) Å, a = 92.078(9)°, β = 104.78(1)°, γ=100.54(1)°, V = 684.3(2) ų, Z = 2R = 0.0503) and [Pt^IV(OH)₂(ipm)(ippda)]·3H₂O (C 2/c, a = 27.275(6) Å, b=6.954(2) Å, c = 22.331(4) Å, β = 118.30(2)°, V = 3729(2) ų, Z = 8, R = 0.0345) have been solved and refined. The local geometry around the platinum(IV) atom approximates to a typical octahedral arrangement with two added groups (OH and OCH₃; OH and OH) in a transposition. The platinum(IV) compounds with potential labile moieties may be important intermediate species for further reactions.     

Syntheses,crystal structures,and characterizations of two novel cubane-like and double cubane-like molybdenum-copper-sulphur clusters {MoCu3S3(S2COEt)}(O)(Ph3P)3 and {Mo2Cu6S6(SCMe3)2}(O)2(Ph3P)4

Two novel heterometallic cubane-like and double cubane-like clusters, {MoCu₃S₃(S₂COEt)}(O)(Ph₃P)₃ I and {Mo₂Cu₆S₆(SCMe₃)₂}(O)₂(Ph₃P)₄ II, were synthesized by reaction of {MoCu₂S₃}(O)(Ph₃P)₃ with CuS₂COEt and CuSCMe₃, respectively. ClusterI crystallized in the triclinic space group (2) witha=12.766(6) Å,b=22.904(5) Å,c=10.522(3) Å, =99.86(2)°, =109.68(2)°, =86.84(3)°,V=2854(2) ų,Z=2,R=0.049 for 6622 observed reflections (I>5(I)) and 410 variables. ClusterII crystallized in the triclinic space group (2) with dimensionsa=14.212(4) Å,b=14.725(5) Å,c=12.396(8) Å, =110.32(4)°, =90.40(5)°, =62.88(2)°,V=2129(2) ų,Z=1,R=0.039 for 6020 observed reflections (I>3(I)) and 461 variables. ClusterI consists of a neutral cubane-like molecule with the core {MoCu₃S₃(S₂COEt)}²⁺, in which one corner of the cubane-like core is a novel triply bridging bidentate 1,1-dithiolato (xanthate, S₂COEt^–) ligand. ClusterII is a double cubane-like one, in which two cubane-like cores {MoCu₃S₃(SCMe₃)}²⁺ are connected by two Cu-S bonds of the triply bridging monothiolato (SCMe ₃ ^– ) ligand. Two different pathways of unit construction from a small heterometallic cluster {MoCu₂S₃}(O)(Ph₃P)₃ have been outlined. Comparisons of the selected bond lengths and bond angles for the cubane-like core {MoCu₃S₃ X} (X=Cl^–, Br^–, S₂COEt^–, SCMe ₃ ^– ) are given. Spectroscopic properties of the title clusters are also reported.     

Cluster synthesis 37—Platinum-ruthenium carbido-cluster complexes: The syntheses and structural characterizations of PtRu5(C)(CO)16, Pt2Ru5(C)(CO)13(COD)2, and Pt3Ru5(C)(CO)14(COD)2

From the reaction of [Ru₅(C)(CO)₁₄]^2– with Pt(COD)Cl₂, COD=1, 5 cyclooctadiene, the new platinum-ruthenium carbido cluster complex PtRu₅ (C)(CO)₁₄(COD),1, was obtained in 41% yield. When1 was allowed to react with carbon monoxide (25°C/1 atm), the new complex PtRu₅(C)(CO)₁₆,2, was obtained almost quantitatively (97% yield). Compound2 was characterized by IR and single-crystal X-ray diffraction analysis. The six metal atoms are arranged in the form of an octahedron with the carbide ligand located in the center. Compound1 is believed to have a similar structure to2 except for a COD ligand coordinated to the platinum atom. When activated by treatment with Me₃NO, compound2 reacts with Pt(COD)₂ at 25°C to yield two higher nuclearity cluster complexes, Pt₂Ru₅C(CO)₁₃(COD)₂.3, and Pt₃Ru₅C(CO)₁₄(COD)₂,4. The structure of3 is similar to that of1, but contains a Pt(COD) grouping capping one Ru₃ triangle of the PtRu₅ octahedron. The structure of4 consists of a PtRu₅ octahedron with two Pt(COD) capping groups, one on an Ru₃ triangle and the other on a PtRu₂ triangle of the octahedron. Crystal data: for2, space group=P2₁/n,a=9.341 (2) Å,b=14.957 (3) Å,c=36.80 (1) Å, =90.38 (2) °,Z=8, 4034 reflections,R=0.030, for3, space group=P2₁/c,a=14.998 (3) Å,b=10.288 (3) Å,c=26.581 (7) Å, =102.75 (2) °,Z=4, 2917 reflections,R=0.028. for4, space group=P2₁/n,a=13.412 (4) Å,b=16.252 (4) Å,c=20.107 (4) Å, =106.13 (2) °,Z=4, 2745 reflections,R=0.032.     

Heterotri- and -tetrametallic alkoxides of chromium(III) containing aluminium(III), gallium(III) and niobium(V)

CrCl₃ · 3THF reacts with two equivalents of potassium alkoxometallates K{M(OPr ⁱ ) _x } [M = Al(A), Ga(B), x = 4; M = Nb(C), x = 6] to give heterobimetallic chloride isopropoxides [Cr{M(OPr ⁱ ) _x }₂Cl(THF)] [M = Al(A – 1), Ga(B – 1), and Nb(C – 1)], in which the replacement of the chloride with an appropriate alkoxometallate (tetraisopropoxoaluminate, tetraisopropoxogallate, or hexaisopropoxoniobate) results in the formation of novel heterotrimetallic derivatives. The 'single pot synthesis of an heterotetrametallic isopropoxide [Cr{Nb(OPr ⁱ )₆}{Al(OPr ⁱ )₄}{Ga(OPr ⁱ )₄}] (7) has been carried out by the sequential addition of (A), (B), and (C) to a benzene suspension of CrCl₃ · 3THF. Alcoholysis of [Cr{Al(OPr ⁱ )₄}₂{Nb(OPr ⁱ )₆}] (1) and [Cr{Al(OPr ⁱ )₄}₂{Ga(OPr ⁱ )₄}] (5) with t-BuOH has also been studied and the derivatives characterized by elemental analyses, molecular weight determinations, spectroscopic [Electronic, i.r., ²⁷Al-n.m.r.] and magnetic susceptibility studies.     

Synthesis and characterization of 4,4′-methylenebis (2,6-di-tert-butylphenol) derivatives of a series of metal alkoxides and alkyls

Investigation of the coordination behavior of 4,4′-methylenebis(2,6-di-tert-butylphenol) (or H₂-4DBP) with a series of metal alkoxides led to isolation of [(OR)₃M]₂(µ-4DBP), where M/OR?=?Ti/OBu^t (2), Ti/ONep (3), Zr/OBu^t (4), Hf/OBu^t (5), and [(py)(OR)₃M]₂(µ-4DBP)?·?py (5a), where py?=?pyridine and ONep?=?OCH₂C(CH₃)₃. Metal alkyl derivatives of 4DBP were also studied and found to form similar di-substituted species: [(py)₂(Et)Zn]₂(µ-4DBP)?·?py (6), [(THF)₃(Br)Mg]₂(µ-4DBP) (7), [(THF)₂(Br)Mg](µ-4DBP)[Mg(Br)(THF)₃]?·?(THF, tol) (7a), and [(py)(R)₂Al]₂(µ-4DBP), where R?=?CH₃ (8), Et (9), CH₂CH(CH₃)₂ (10); tol?=?toluene and THF?=?tetrahydrofuran. All structures demonstrate the bridging nature of 4DBP and the ability to bind a variety of metal centers. Solution state NMR indicates that the structures of 2–10 are retained in solution. Thermal analyses indicate that 4DBP is preferentially lost during heating.     

Synthesis, Molecular Structure and Derivatization of the Triruthenacarborane Cluster Compound [1-SMe2-2,2-(CO)2-7,11-(Μ-H)2-2,7,11-{Ru2(CO)6}-closo-2,1-RuCB10H8]*

In toluene at reflux temperatures [Ru₃(CO)₁₂] and 7-SMe₂-nido-7-CB₁₀H₁₂ give the charge-compensated cluster complex [1-SMe₂-2,2-(CO)₂-7,11-(μ-H)₂-2,7,11-Ru₂(CO)₆-closo-2,1-RuCB₁₀H₈] (1) . Treatment of 1 with dppm in THF affords [1-SMe₂-2,2-(CO)₂-7,11-(μ-H)₂-2,7,11-Ru₂(μ -dppm)(CO)₄-closo-2,1-RuCB₁₀H₈] (2) [dppm = bis(diphenylphosphino)methane; THF = tetrahydrofuran]. The latter complex on heating in THF with [ ]F yields the salt [ ][1-SMe-2,2-(CO)₂-7,11-(μ-H)₂-2,7,11-Ru₂(μ -dppm)(CO)₄-closo-2,1-RuCB₁₀H₈] (3). Reaction of 3 with [AuCl(PPh₃)] and Tl[PF₆] gives the neutral zwitterionic complex [1-S(Me)Au (PPh₃)-2,2-(CO)₂-7,11-(μ-H)₂-2,7,11-Ru₂(μ-dppm)(CO)₄-closo-2,1-RuCB₁₀H₈] (4). The structures of 1, 3 and 4 were determined by single-crystal X-ray diffraction studies.*Dedicated to Professor F. Albert Cotton on the occasion of his 75th birthday, in appreciation of our long friendship and in recognition of his outstanding contributions to the study of complexes with metal–metal bonds.     

Lutetium complexes with tetraphenylethylene dianion. Synthesis and structure

The reactions of dipotassium and disodium salts of the tetraphenylethylene dianion with LuCl₃(THF)₃ or CpLuCl₂(THF)₃ yielded the homoleptic ate-complexes [Na(THF)₅][Lu(Ph₂CCPh₂)₂] (1) and [K(THF)₅][Lu(Ph₂CCPh₂)₂] (2) or the heteroleptic complex CpLu(Ph₂CCPh₂)(THF)₂ (4), respectively. Recrystallization of complex 1 from a diglyme—THF mixture afforded [Na(diglyme)₂][Lu(Ph₂CCPh₂)₂](THF)_0,5 (3). Recrystallization of complex 4 from 1,2-dimethoxyethane gave [CpLu(Ph₂CCPh₂)(DME)](DME) (5). The structures of complexes 3 and 5 were established by X-ray diffraction analysis. In both complexes, the unusual η⁶-coordination of the (Ph₂CCPh₂)²⁻ dianion to lutetium is observed. The Lu-C distances vary from 2.441(2) to 2.643(2) Å (3) and from 2.470(3) to 2.763(3) Å (5). In complexes 3 and 5, a redistribution of the C-C bond lengths was observed in the Ph groups coordinated to lutetium. Studies by ¹H, ¹³C, and 2D NMR spectroscopy demonstrated that the η⁶-coordination of the tetraphenylethylene dianion in homoleptic ate-complexes 1 and 2 is retained in a THF solution, whereas the coordination of this dianion in heteroleptic complex 4 changes from η⁶ to η⁴.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2060–2068, October, 2004.