Slow relaxation of the magnetization in high-nuclearity Ln-complexes

By the surface modification strategy, a novel high-nuclearity lanthanide complex with a discrete structure, Er₂₆I(μ₃-OH)₂₀(μ₃-O)₆(NO₃)₉(IN)₃₃(OH)₃(H₂O)₃₃ (noted Er₂₆, HIN = isonicotinic acid), has been prepared under hydrothermal conditions. The magnetic properties of Er₂₆ and two analogue dysprosium assemblies Dy₃₀I(μ₃-OH)₂₄(μ₃-O)₆(NO₃)₉(IN)₄₁(OH)₃(H₂O)₃₈ (noted Dy₂₆-I) and Dy₂₆I(μ₃-OH)₂₀(μ₃-O)₆(NO₃)₉(IN)_31.25(OH)_4.75(H₂O)_41.75 (noted Dy₂₆-II) have been studied. The results show that the slow relaxation of the magnetization is newly found in Dy₂₆-I constructed from {Dy₂₆} and {Dy₄} cluster units. The {Dy₄} units in Dy₂₆-I, the relative orientation of the complex or the inter-molecular interactions between {Dy₂₆} cores might play an important role in the origin of this magnetic behavior.     

Extending the coordination chemistry of cobalt with the metalloligand [Pt2(μ-S)2(PPh3)4]: Synthesis of the first cobalt(III) derivatives

The coordination chemistry of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] towards cobalt(II) and cobalt(III) centres has been explored using an electrospray ionisation mass spectrometry (ESI MS)-directed methodology. Reaction of [Pt₂(μ-S)₂(PPh₃)₄] with CoCl₂·6H₂O in methanol gave a green-yellow suspension of the known adduct [Pt₂(μ-S)₂(PPh₃)₄CoCl₂], and the CoBr₂ adduct could be similarly prepared. When in situ-generated [Pt₂(μ-S)₂(PPh₃)₄CoCl₂] is reacted with 8-hydroxyquinoline (HQ) and base, the initial product is the cobalt(II) adduct [Pt₂(μ-S)₂(PPh₃)₄CoQ]⁺, which is then converted in air to the cobalt(III) adduct [Pt₂(μ-S)₂(PPh₃)₄CoQ₂]⁺, isolated as its hexafluorophosphate salt. The corresponding picolinate (Pic) derivative [Pt₂(μ-S)₂(PPh₃)₄Co(Pic)₂]⁺ was similarly prepared, however reaction of [Pt₂(μ-S)₂(PPh₃)₄], CoCl₂·6H₂O and 8-(tosylamino)quinoline (HTQ) produced only the cobalt(II) adduct [Pt₂(μ-S)₂(PPh₃)₄CoTQ]⁺. Reactions of [Pt₂(μ-S)₂(PPh₃)₄], CoCl₂·6H₂O and dithiocarbamates gave cobalt(III) complexes [Pt₂(μ-S)₂(PPh₃)₄Co(S₂CNR₂)₂]⁺ [R = Et or R₂ = (CH₂)₄], and proceeded much more rapidly, consistent with the known ability of the dithiocarbamate ligand to stabilize cobalt in higher oxidation states. A study of the fragmentation of cobalt(III) adducts by positive-ion ESI mass spectrometry indicated that [Pt₂(μ-S)₂(PPh₃)₄CoQ₂]⁺ fragments to form the radical cation [Pt₂(μ-S)₂(PPh₃)₄]⁺, which could also be generated by ESI MS analysis of [Pt₂(μ-S)₂(PPh₃)₄] in methanol-NaOH solution. In contrast, the corresponding indium(III) derivative [Pt₂(μ-S)₂(PPh₃)₄InQ₂]⁺, and the cobalt(III) dithiocarbamate [Pt₂(μ-S)₂(PPh₃)₄Co(S₂CN(CH₂)₄)₂]⁺ are much more reluctant to fragment under analogous conditions, and the differences are discussed in terms of cobalt(III) redox chemistry.     

Hydrothermal syntheses and structures of vanadium oxyfluorides templated by organic and metal organic cations

The hydrothermal reactions of V₂O₅, HF and an organodiphosphonic acid, in the presence of appropriate templating organoammonium or metal-organic complex cations provided three new oxyfluorovanadate compounds. The V(IV) species [H₃N(CH₂)₂NH₂(CH₂)₂NH₂(CH₂)₂NH₃][V₃O₃F₂(H₂O){O₃PCH₂PO₃}₂]·2H₂O (1·2H₂O) exhibits a three-dimensional anionic framework constructed from {VO(O₃PCH₂PO₃)}_n²ⁿ⁻ chains and {VF₂O₄} octahedra. The molecular structure of [N(CH₂CH₂NH₃)₃]₂[NH₄][V₃O₂F₆(O₃PCH₂PO₃)₂]·2H₂O (2·2H₂O) is characterized by the presence of unique {V₃O₂F₆(O₃PCH₂PO₃)₂}⁷⁻ clusters. The bimetallic phase [{Cu(ophen)}VOF{HO₃P(CH₂)₅PO₃}] (3) is one-dimensional with {Cu₂V₂O₂F₂(HO₃PR)₂(O₃PR)₂} cluster building blocks.     

Syntheses, structures and electrochemical study of π-acetylene complexes of cobalt

The preparation and characterisation of the complexes [Co₂(CO)₄(PMe₃)₂][Co₂(CO)₆](Me₃SiC₂C₂SiMe₃) (4), [Co₂(CO)₄(dppm)][Co₂(CO)₆](Me₃SiC₂C₂H) (5), [Co₂(CO)₄(dppa)][Co₂(CO)₆](Me₃SiC₂C₂SiMe₃) (6), [Co₂(CO)₄(dppm)]₂[Co₂(CO)₆](Me₃SiC₂CCC₂C₂SiMe₃) (7) and [{SiMe₃(Co₂(CO)₄(dppm))C₂}₂(HCC)(1,3,5-C₆H₃)] (8) are described. An electrochemical study of the complexes 5-8 and of the related [Co₂(CO)₄(dppm)]₂(Me₃SiC₂(CC)₂C₂SiMe₃) (1), [Co₂(CO)₄(dppa)]₂(Me₃SiC₂C₂SiMe₃) (2) and [{SiMe₃(Co₂(CO)₄(dppm))C₂}(HCC)₂(1,3,5-C₆H₃)] (3) is presented by means of the cyclic and square-wave voltammetry techniques. Crystals of 8 suitable for single-crystal X-ray diffraction were grown and the molecular structure of this compound is discussed.     

Solution-phase disproportionation equilibria for monosubstituted Pentakis- (arylisocyanide)cobalt(I) complexes by proton-NMR studies

Equilibrium constants, K_dis, for the solvent- dependent, solution-phase disproportionation equilibria of monosubstituted pentakis(arlisocyanide)cobalt(I) complexes: 2[Co(CNR)₄L]⁺?[Co(CNR)₃L₂]⁺ + [Co(CNR)₅]⁺, K_dis = $\text{[Co(CNR)}{}_3\text{L}{}_2\text{][Co(CNR)}{}_5\text{]}\text{[Co(CNR)}{}_4\text{L]}{}^2$ are measured by planimeter-integration of proton- NMR spectra at ambient temperature. The complexes, [Co(CNR)₄L]ClO₄, R = 2,6-Me₂C₆H₃, L = P(C₆H₅)₃, P(C₆H₄Cl-p)₃, P(OC₆H₅)₃, P(OC₆H₄Cl-p)₃; R = o-MeC₆H₄, L = P(C₆H₄Cl-p)₃, P(OC₆H₅)₃, P(OC₆H₄Cl-p)₃; R = 2,4,6-Me₃C₆H₂, L = P(C₆H₅)₃; R = 2,6-Et₂C₆H₃, L = P(C₆H₅)₃; are investigated in the deuterated solvents, CDCl₃, CD₃CN, (CD₃)₂CO, C₅D₅N, CD₃NO₂, and (CD₃)₂SO. Disproportionation seems to occur in all [Co(CNR)₄L]⁺, but NMR study is facilitated by utilizing equivalent alkyl protons (i.e., Me-groups) on the RNC ligands.Correlation of K_dis values with steric-hindrance of the RNC in sets of complexes with the same P-ligand is evident in all solvents: K_dis decreases with increased steric-hindrance in RNC. The K_dis values for complexes with the same RNC and analogous triarylphosphine, triarylphosphite ligands (i.e., PR₃, P(OR)₃, same R) are approximately equal. The K_dis values for complexes of P-ligands with Cl-substituent are significantly larger than K_dis values for complexes with the corresponding unsubstituted P-ligands (e.g., [Co(CNR)₄P(C₆H₄Clp)₃]ClO₄vs. [Co(CNR)₄P(C₆H₅)₃]ClO₄) in (CD₃)₂CO and C₅D₅N solution, but are smaller in CDCl₃ and CD₃CN, and approximately equal in CD₃NO₂ and (CD₃)₂SO. Properties of the solvents are also considered.     

Effect of copper-substitution on the structure and nuclearity of Cu(II)-pyrazolates: from trinuclear to tetra-, hexa- and polynuclear complexes

The influence of terminal ligands on the structure and nuclearity of copper(II)-pyrazolates has been investigated. Exchange of the chloride ligands of [Cu₃(μ₃-X)(μ-pz)₃Cl₃]ⁿ⁻ (X=O, OH; n=2, 1) or [Cu₃(μ₃-Cl)₂(μ-pz)₃Cl₃]²⁻ complexes for cyanate, acetate or bromide ligands maintains the integrity of the triangular species: PPN[Cu₃(μ₃-OH)(μ-pz)₃(NCO)₃], PPN[Cu₃(μ₃-OH)(μ-pz)₃(O₂CCH₃)₃(H₂O)] · H₂O, Bu₄N[Cu₃(μ₃-OH)(μ-pz)₃(O₂CCH₃)₃] · 3H₂O and (Bu₄N)₂[Cu₃(μ₃-Br)₂(μ-pz)₃Br₃] have been prepared and characterized by spectroscopic and X-ray diffraction techniques, respectively. In contrast, tetranuclear complexes (Bu₄N)₂[Cu₄(μ₃-OH)₂(μ-4-X-pz)₂(μ-O₂CPh)₂(O₂CPh)₄] (X=H, Cl, Br, NO₂) and the hexanuclear complex (Bu₄N)₂[Cu₆(μ₃-O)(μ₃-OH)(μ-4-NO₂-pz)₆(μ-O₂CPh)₃(O₂CPh)₂(H₂O)] · (CH₂Cl₂)_0.5 have been obtained on substitution for benzoate ligands. An attempt to partially substitute the chlorides for tert-butoxide ligands, also provided a tetranuclear complex, (Bu₄N)₂[Cu₄(μ-OH)₂(μ-pz)₄Cl₄], without incorporation of the incoming ligand. Similarly, removal of all chloride ions in the absence of an appropriate substituting ligand leads to higher nuclearity metallacycles [Cu(μ-OH)(μ-pz)]_n (n=6, 8, 9, 12, 14).     

Coordination chemistry of copper-molybdates with alkoxide ligands: The {Mo4O10(OMe)6} and [Mo2O4{RC(CH2O)3}2] clusters as building blocks

The reactions of the Keplerate super cluster [Mo₁₃₂O₃₇₂(CH₃CO₂)₃₀(H₂O)₇₂]⁴²⁻ with a Cu(II) source and an organonitrogen donor in methanol/DMF solutions yielded a series of bimetallic organic-inorganic oxide hybrid materials, including the molecular species [Cu(phen)₂MoO₄] (1) and [{Cu(terpy)}₂(MoO₄)₂] (2) and a series of materials constructed from the tetranuclear building block {Mo₄O₁₀(OMe)₆}²⁻: the molecular [{Cu₂(phen)₂(O₂CCH₃)₂ (MeOH)}Mo₄O₁₀(OMe)₆] (3), [{Cu(terpy)(O₂CCH₃)}₂Mo₄O₁₀(OMe)₆] (4) and [{Cu(terpy)Cl}₂Mo₄O₁₀(OMe)₆] (5), the one-dimensional phases [{Cu(bpy)(HOMe)₂}Mo₄O₁₀(OMe)₆] (6), [{Cu(bpy)(DMF)₂}Mo₄O₁₀(OMe)₆] (7), [{Cu(bpa)(DMF)₂}Mo₄O₁₀(OMe)₆] (8), [{Cu(phen)(DMF)₂}Mo₄O₁₀(OMe)₆] (9) and [{CuCl(dpa)}₂Mo₄O₁₀(OMe)₆] (10), and the two-dimensional material [{Cu₂(DMF)₂(pdpa)}{Mo₄O₁₀(OMe)₆}₂] (11). When methanol is replaced by the tridentate alkoxide tris-methoxypropane (trisp), the {Mo₂O₄(trisp)₂}²⁻ cluster building block is observed for [Cu(phen)Mo₂O₄(trisp)₂] (12), [Cu(bpa)(DMF)Mo₂O₄(trisp)₂] (13) and [{Cu(bpy)(NO₃)}₂Mo₂O₄(trisp)₂] (14).     

Thallium(III) complexes of the metalloligands [Pt2(μ-S)2(PPh3)4] and [Pt2(μ-Se)2(PPh3)4]

Reactions of [Pt₂(μ-S)₂(PPh₃)₄] with the diarylthallium(III) bromides Ar₂TlBr [Ar = Ph and p-ClC₆H₄] in methanol gave good yields of the thallium(III) adducts [Pt₂(μ-S)₂(PPh₃)₄TlAr₂]⁺, isolated as their salts. The corresponding selenide complex [Pt₂(μ-Se)₂(PPh₃)₄TlPh₂]BPh₄ was similarly synthesised from [Pt₂(μ-Se)₂(PPh₃)₄], Ph₂TlBr and NaBPh₄. The reaction of [Pt₂(μ-S)₂(PPh₃)₄] with PhTlBr₂ gave [Pt₂(μ-S)₂(PPh₃)₄TlBrPh]⁺, while reaction with TlBr₃ gave the dibromothallium(III) adduct [Pt₂(μ-S)₂(PPh₃)₄TlBr₂]⁺[TlBr₄]⁻. The latter complex is a rare example of a thallium(III) dihalide complex stabilised solely by sulfur donor ligands. X-ray crystal structure determinations on the complexes [Pt₂(μ-S)₂(PPh₃)₄TlPh₂]BPh₄, [Pt₂(μ-S)₂(PPh₃)₄TlBrPh]BPh₄ and [Pt₂(μ-S)₂(PPh₃)₄TlBr₂][TlBr₄] reveal a greater interaction between the thallium(III) centre and the two sulfide ligands on stepwise replacement of Ph by Br, as indicated by shorter Tl-S and Pt?Tl distances, and an increasing S-Tl-S bond angle. Investigations of the ESI MS fragmentation behaviour of the thallium(III) complexes are reported.     

Syntheses and structures of the heterometallic clusters [(Ph3PAu)3Re(CO)4], [(Ph3PAu)4Re(CO)4], [(Ph3PAu)6AuRe2(CO)8], and [(Ph3PAu)6Re(CO)3]

The reaction of [HRe₃(CO)₁₂]²⁻ with an excess of Ph₃PAuCl in CH₂Cl₂ yields [(Ph₃PAu)₄Re(CO)₄]⁺ as the main product, which crystallizes as [(Ph₃PAu)₄Re(CO)₄]PF₆ · CH₂Cl₂ (1 · CH₂Cl₂) after the addition of KPF₆.The crystal structure determination reveals a trigonal bipyramidal Au₄Re cluster with the Re atom in equatorial position.If [(Ph₃PAu)₄Re(CO)₄]⁺ is reacted with PPh₄Cl, a cation [Ph₃PAu]⁺ is eliminated as Ph₃PAuCl, and the neutral cluster [(Ph₃PAu)₃Re(CO)₄] (2) is formed.It combines with excess [(Ph₃PAu)₄Re(CO)₄]⁺ to afford the cluster cation, [(Ph₃PAu)₆AuRe₂(CO)₈]⁺. It crystallizes from CH₂Cl₂ as[(Ph₃PAu)₆AuRe₂(CO)₈]PF₆ · 4CH₂Cl₂ (3 · 4CH₂Cl₂). In [(Ph₃PAu)₃Re(CO)₄] the metal atoms are arranged in form of a lozenge while in [(Ph₃PAu)₆AuRe₂(CO)₈]⁺ two Au₄Re trigonal bipyramids are connected by a common axial Au atom.The treatment of [(Ph₃PAu)₄Re(CO)₄]⁺ with KOH and Ph₃PAuCl in methanol yields the cluster cation [(Ph₃PAu)₆Re(CO)₃]⁺, which crystallizes with from CH₂Cl₂ as [(Ph₃PAu)₆Re(CO)₃]PF₆ · CH₂Cl₂ (4 · CH₂Cl₂). The metal atoms in this cluster form a pentagonal bipyramid with the Re atom in the axial position.     

Insertion reactions of 1,4-diisocyanobenzene in binuclear Pd(I) complexes

Reactions between XPd(μ-dmp)₂PdX′ (X = X′ = Cl, Br, I, NCO, SCN, N₃ or C₆F₅; X = C₆F₅, X′ = Cl, Br, I, NCO) with 1,4-diisocyanobenzene lead to the tetranuclear complexes [(μ,μ′-CNC₆H₄NC){XPd(μ-dpm)₂PdX′}₂], where both ends of the diisocyanide are inserted in a metalmetal bond. The cationic derivatives [(μ,μ′-CNC₆H₄NC){(RNC)Pd(μ-dpm)₂(CNR)}₂](BPh₄)₄ and [(μ,μ′-CNC₆H₄NC){(RNC)Pd(μ-dpm)₂Pd(C₆F₅)}₂] (BPh₄)₂ (R = p-Tol, Cy, or ^tBu) are obtained by reacting [(μ,μ′-CNC₆H₄NC){ClPd(μ-dpm)₂PdX}₂] (X= Cl or C₆F₅) with RNC in the presence of NaBPh₄. Treatment of [(μ,μ′-CNC₆H₄NC){ClPd(μ-dpm)₂Pd(C₆F₅)}]₂ with NaBPh₄ causes the di-insertion and subsequent coordination of the isocyanide, yielding [(C₆F₅)Pd(CN-C₆H₄NC) Pd(μ-dpm)₂Pd(C₆F₅)](BPh₄)₂.     

Influence of chain length on mono- versus di-alkylation in the reactivity of [Pt2(μ-S)2(PPh3)4] towards α,ω-dihalo-n-alkanes; a synthetic route to platinum(II) ω-haloalkylthiolate complexes

The reactions of [Pt₂(μ-S)₂(PPh₃)₄] with α,ω-dibromoalkanes Br(CH₂)_nBr (n = 4, 5, 6, 8, 12) gave mono-alkylated [Pt₂(μ-S){μ-S(CH₂)_nBr}(PPh₃)₄]⁺ and/or di-alkylated [Pt₂(μ-S(CH₂)_nS}(PPh₃)₄]²⁺ products, depending on the alkyl chain length and the reaction conditions. With longer chains (n = 8, 12), intramolecular di-alkylation does not proceed in refluxing methanol, with the mono-alkylated products [Pt₂(μ-S){μ-S(CH₂)_nBr}(PPh₃)₄]⁺ being the dominant products when excess alkylating agent is used. The bridged complex [{Pt₂(μ-S)₂(PPh₃)₄}₂{μ-(CH₂)₁₂}]²⁺ was accessible from the reaction of [Pt₂(μ-S)₂(PPh₃)₄] with 0.5 mol equivalents of Br(CH₂)₁₂Br. [Pt₂(μ-S){μ-S(CH₂)₄Br}(PPh₃)₄]⁺ can be cleanly isolated as its BPh₄⁻ salt, but undergoes facile intramolecular di-alkylation at −18 °C, giving the known species [Pt₂(μ-S(CH₂)₄S}(PPh₃)₄]²⁺. The reaction of I(CH₂)₆I with [Pt₂(μ-S)₂(PPh₃)₄] similarly gives [Pt₂(μ-S){μ-S(CH₂)₆I}(PPh₃)₄]⁺, which is fairly stable towards intramolecular di-alkylation once isolated. These reactions provide a facile route to ω-haloalkylthiolate complexes which are poorly defined in the literature. X-ray crystal structures of [Pt₂(μ-S){μ-S(CH₂)₅Br}(PPh₃)₄]BPh₄ and [Pt₂(μ-S(CH₂)₅S}(PPh₃)₄](BPh₄)₂ are reported, together with a study of these complexes by electrospray ionisation mass spectrometry. All complexes fragment by dissociation of PPh₃ ligands, and the bromoalkylthiolate complexes show additional fragment ions [Pt₂(μ-S){μ-S(CH₂)_n−2CHCH₂}(PPh₃)_m]⁺ (m = 2 or 3; m ≠ 4), most significant for n = 4, formed by elimination of HBr.     

A New Basic Triple Salt Containing Magnesium Hydroxide

The quinary system KCl-K₂SO₄-MgCl₂-MgSO₄-Mg(OH)₂-H₂O and associated eight systems K₂SO₄-MgSO₄-Mg(OH)₂-H₂O, MgCl₂-MgSO₄-Mg(OH)₂-H₂O, KCl-MgCl₂-Mg(OH)₂-H₂O, KCl-K₂SO₄-Mg(OH)₂-H₂O, MgSO₄-Mg(OH)₂-H₂O, MgCl₂-Mg(OH)₂-H₂O, K₂SO₄-Mg(OH)₂-H₂O and KCl-Mg(OH)₂-H₂O were investigated at 50° The solid phases of these systems were the new basic triple salt (NS salt B), MgCl₂ · 3Mg(OH)₂ · 8H₂O, MgSO₄ · 5Mg(OH)₂ · 3H₂O, carnallite, leonite, kieserite, hexahydrite, bischofite, potassium chloride, potassium sulfate and magnesium hydroxide and the crystallization fields of these salts in nine systems were determined.     

Formation of cyclo- and polystannanes by dehydrogenative stannane coupling catalyzed by platinum(II) complexes

Reaction of (PhMe₂P)₂PtMe₂ or [(κ²-P,N)-Ph₂PC₂H₄NMe₂]PtMe₂ with an excess of H₂SnBu₂ or H₂SnPh₂ resulted in the catalytic formation of cyclo-, oligo- and/or polystannanes. In the reaction of (PhMe₂P)₂PtMe₂ with H₂SnBu₂, linear oligomeric species H(SnBu₂)_nH were observed in the initial stage of the reaction, which eventually converted into cyclostannanes. Only polystannanes were observed in the reaction of [(κ²-P,N)-Ph₂PC₂H₄NMe₂]PtMe₂ with H₂SnBu₂. The reactions of H₂SnPh₂ were similar, but more difficult to analyze due to redistribution reactions and the formation of insoluble products. The mechanism of the reactions is clearly different to that previously observed for HSnR₃ because metal complexes indicative of oxidative addition/reductive elimination reactions were only observed as minor products.     

The Amino Acid Composition of Human Pituitary Growth Hormone

The amino acid content in human hypophyseal growth hormone has been determined by chromatography on resin columns. On the basis of 29,000 for the molecular weight, the empirical formula of the hormone was obtained: lys₁₃his₅arg₁₄asp₂₇ thr₁₄ser₂₃glu₃₄pro₁₂gly₁₃ala₁₂-(1/2 cys)₆val₁₂met₄-ileu₁₀leu₃₁tyr₁₀phe₁₅try₁(NH₃)₃₂.     

Synthesis, crystal structure and vibrational spectroscopy of a novel mixed ligands Ni(II) pentaborate: [Ni(C4H10N2)(C2H8N2)2][B5O6(OH)4]2

A novel organic-inorganic hybrid pentaborate [Ni(C₄H₁₀N₂)(C₂H₈N₂)₂][B₅O₆(OH)₄]₂ has been synthesized by hydrothermal reaction and characterized by FT-IR, Raman spectroscopy, elemental analyses and DTA-TGA. Its crystal structure was determined from single crystal X-ray diffraction. The structure consists of isolated polyborate anion [B₅O₆(OH)₄]⁻ and nickel complex cation of [Ni(C₄H₁₀N₂)(C₂H₈N₂)₂]²⁺, in which the two kinds of ligands come from the decomposition of triethylenetriamine material. The [B₅O₆(OH)₄]⁻ units are connected to one another through hydrogen bonds, forming a three-dimensional framework with large channel along the a and c axes, in which the templating [Ni(C₄H₁₀N₂)(C₂H₈N₂)₂]²⁺ cations are located. The assignments of the record FT-IR absorption frequencies and Raman shifts were given.     

Raman and infrared spectroscopic and theoretical studies of dinuclear rhenium and osmium complexes, M2(O2CCH3)4X2 (M = Re, Os; X = Cl, Br)

Infrared, far-infrared and Raman spectra of Re₂(O₂CCH₃)₄X₂ (X = Cl, Br) and Re₂(O₂CCD₃)₄Cl₂ have been recorded. Assignments of the vibrational spectra of Os₂(O₂CCH₃)₄Cl₂ and its deuterated derivative have been completed together with the Re complexes on the basis of normal-coordinate analysis. Force constant calculation was made for the acetate ion as well as for a four-atomic unit (with the CH₃ and CD₃ groups considered as point masses) using optimized masses of 16.7, 17.8, 20.5 and 21.6 for ¹²CH₃, ¹³CH₃, ¹²CD₃ and ¹³CD₃ groups, respectively. The force constants of the acetate ion have been adopted to the starting force field of the M₂(O₂CCH₃)₄X₂ type complexes. The metal-halide (0.889, 0.997 and 1.286 N cm⁻¹) and metal-metal stretching (3.32, 3.34 and 3.57 N cm⁻¹) force constants were obtained for Re₂(O₂CCH₃)₄Cl₂Re₂(O₂CCH₃)₄Br₂ and Os₂(O₂CCH₃)₄Cl₂ complexes, respectively. It was shown that the so-called diatomic approximation in most cases overestimates the M-M stretching force constants by 30-40%. Much better correlation has been obtained to fit these force constants, which produced values very close to those obtained by full normal-coordinate calculations. The Re-Re stretching force constants showed a reasonable correlation with the Re-Re bond distances for 18 rhenium complexes.     

Synthesis, spectroscopic and structural characterization of Cu(II) derivatives of tris(pyrazol-1-yl)methanes

The reaction between CuX₂ (X=ClO₄, NO₃, Cl, Br and CH₃COO) and excess of tris(pyrazol-1-yl)methane ligands L (L=CH(pz)₃, CH(4-Mepz)₃, CH(3,5-Me₂pz)₃, CH(3,4,5-Me₃pz)₃ or CH(3-Mepz)₂(5-Mepz)) yields [CuX₂(L)], [{CuX₂}₃(L₂)₂] or [Cu(L₂)]X₂-type complexes. The ligand to metal ratio is dependent on the number and disposition of the Me substituents on the azole-type ligand and mainly on the nature of the counter-ion X. All complexes have been characterized in the solid state as well as in solution (IR and UV spectra, and conductivity determinations). The solid-state structures of [Cu{(3,5-Me₂pz)₃CH}₂](NO₃)₂, [Cu{(3,5-Me₂pz)₃CH}₂](ClO₄)₂·0.5H₂O, [Cu{(3,4,5-Me₃pz)₃CH}₂](NO₃)₂·H₂O, [Cu{(4-Mepz)₃CH}₂]Br₂·3H₂O have been determined by single crystal X-ray studies.     

Preparation of mono- or di-metal indenyl-iridium edrivatives and of tri-metal iridium-platinum complexes

Treatment of [IrCl(C₂H₄)₄] with K(C₉H₇) (C₉H₇ =indenyl) gives [Ir(C₂H₄)₂(η-C₉H₇)]. This compound is converted quantitatively into [Ir(CO)₂(η-C₉H₇)] by treatment with carbon monoxide. By reacting together these two iridium complexes [Ir₂(μ-CO)(CO)₂(ηC₉H₇)₂] has been obtained. The compound [Ir(CO)₂(η-C₉H₇)] reacts with [Pt(C₂H₄)₂{P(cyclo-C₆H₁₁)₃}] to give the complex [Ir₂Pt(CO)₃{P(cyclo-C₆H₁₁)₃}(η-C₉H₇)₂]. Protonation of the latter affords the salt [Ir₂Pt(μ-H)(CO)₃{P(cyclo-C₆H₁₁)₃}(μ-C₉H₇)₂] [BF₄]. The main features of the molecular structure of these complexes have been established by IR and NMR spectroscopy.     

Syntheses and michael additions to vinylidene diphosphine complexes of type [M(CO)4{(Ph2P)2CCH2}] (MCr,Mo or W)

Treatment of [M(CO)₄Ph₂PCHPPh₂]⁻ with CH₃- OCH₂Cl at 20 °C gave the methoxymethyl derivations [M(CO)₄{Ph₂PCH(CH₂OCH₃)PPh₂}] (MCr or W), but a similar treatment at 80 °C gave derivatives of a vinylidene diphosphine [M(CO)₄(Ph₂P)₂C CH₂]. Treatment of [M(CO)₄Ph₂PCHPPh₂]⁻with CH₃CHClOCH₃ at 20 or 80 °C gave only [M(CO)₄- (Ph₂P)₂CHCH(CH₃)OCH₃] (MCr or W). The vinylidene diphosphine complexes [M(CO)₄(Ph₂P)2- CCH₂] (MCr, Mo or W) were even more easily prepared by treating [M(CO)₆] with (Ph₂P)₂CCH₂ (vdpp) in hot solvents such as CH₃OCH₂CH₂OCH₂- CH₂OCH₃.Treatment of [W(CO)₄vdpp] with LiBuⁿ followed by methanol gave [W(CO)₄(Ph₂P)₂CHCH₂Buⁿ] (1c), i.e. conjugate addition to the CCH₂ occurs. 1c was also made by treating [W(CO)₄(Ph₂P)₂CH]⁻ with n-pentyl-iodide. Similarly LiMe was added to [W(CO)₄(Ph₂P)₂CCH₂]. Treatment of [M(CO)₄- vdpp] with NaCH(COOEt)₂ gave [M(CO)₄(Ph₂- P)₂CHCH₂CH(COOEt)₂] (MW or Mo). Pyrrolidine added to the CCH₂ bonds of [M(CO)₄vddp] to give [M(CO)₄(Ph₂P)₂CHCH₂NC₄H₈]. ³¹p and ¹H NMR and IR data are given.     

The structure of (μ3-sulfido)(μ3-p-tolyphosphido)tris(tricarbonyliron)(2FeFe)

Compounds of the type (μ₃-S)(μ₃-RP)Fe₃(CO)₉ have been prepared by the reaction of Fe₃(CO)₁₂ with [RP(S)S]₂ or RP(S)Cl₃. In this paper we report the synthesis of (μ₃-S)(μ₃-CH₃OC₆H₄P)Fe₃(CO)₉ using Lawesson's reagents, and the three dimensional structure of (μ₃-S)(μ₃-p-CH₃C₆H₄P)Fe₃(CO)₉. This material crystallizes in the space group P2₁/n with a = 8.558(2) Å, b = 9.022(2) Å, c = 27.506(6) Å, β = 95.40(2)°, Z = 4. The cluster is a nido structure as found commonly for (μ₃-X)(μ₃-Y)Fe₃(CO)₉ complexes.