Synthesis and reactions of [M(CO)4(Ph2PSiMe3)X] complexes (M = Mn,Re; X = Halogen)

The silylphosphine ligand Ph₂PSiMe₃ reacts readily with a slurry of [Re(CO)₅X] (X  Cl, Br) in polar and in non-polar solvents to yield soluble cis-[Re(CO)₄- (Ph₂PSiMe₃)X] (Ia, X  Cl;Ib, X  Br) via CO substitution. Compound I is readily hydrolyzed by water or silica gel to cis-[Re(CO)₄(Ph₂PH)X]. Compound Ib reacts with [Re(CO)₅Br] to yield [Re₂(CO)₈(μ-PPh₂)- (μ-Br)] (II), and with [Mn(CO)₅Br] to yield [MnRe- (CO)₈(μ-PPh₂)(μ-Br)] (III).The reaction of Ph₂PSiMe₃ with [Mn(CO)₅X] (X=Cl,Br,I) is highly dependent upon reaction conditions.In polar and in non-polar solvents, an excess of ligand gives mainly cis-[Mn(CO)₄(Ph₂PSiMe₃)X] (IVa, X  Cl;IVb, X  Br;IVc, X I). With ligand: [Mn(CO)₅X] reacting ratios in the range 0.5–1.0:1, the products from the three respective halomanganese complexes in THF were: (a) mainly [Mn₂(CO)₈(μ- PPh₂)(μ-Cl) (Va); (b) both [Mn(CO)₄(Ph₂PSiMe₃)Br] and [Mn₂(CO)₈(μ-PPh₂)(μ-Br)] (Vb); and (c) exclusively [Mn(CO)₄(Ph₂PSiMe₃)I]. The compounds IVa-c are stable in solution at ambient temperatures and are readily hydrolyzed by water or methanol to [Mn(CO)₄(Ph₂PH)X]. Compound IVb reacts at room temperature with [Mn(CO)₅Cl] to yield only [Mn₂- (CO)₈(μ-PPh₂)(μ-Br)] (Vb); compound IVc reacts in hot toluene with [Mn(CO)₅Cl] to yield mainly [Mn₂(CO)₈(μ-PPh₂)(μ-I)] (Vc), together with a small amount of the chloro-bridged analog.The dinuclear species II, III and Va-c appear to be formed mainly via an intermolecular elimination of Me₃SiX from the appropriate [M(CO)₄(Ph₂PSiMe₃)X] and metalpentacarbonylhalide (chloride or bromide) complexes.     

Optical activity of dimolybdenum complex induced by chiral,chelating diamine ligand; syntheses and structures of [Mo2(O2CCF3)2(S,S-dach)2(CH3CN)2][BF4]2 and [Mo2(O2CCF3)2(R,R-dach)2(CH3CN)2][BF4]2 (dach=1,2-diaminocyclohexane)

The first structurally characterized, quadruply bonded complexes containing chiral diamine ligands, [Mo₂(O₂CCF₃)₂(S,S-dach)₂(CH₃CN)₂][BF₄]₂ (1), and [Mo₂(O₂CCF₃)₂(R,R-dach)₂(CH₃CN)₂][BF₄]₂ (2); (dach=1,2-diaminocyclohexane) were prepared by reactions of [Mo₂(O₂CCF₃)₂(CH₃CN)₆][BF₄]₂ with S,S-dach and R,R-dach, respectively, in CH₃CN. Their UV–Vis and circular dichroism (CD) spectra have been recorded and their structures determined by X-ray crystallography. Crystals of complexes 1 and 2 conform to the space groups P2 with two independent half molecules in the asymmetric unit. The two molecules have a similar structure consisting of a Mo₂ unit bridged by two cis-trifluoroacetate ligands and chelated by two dach ligands. Two acetonitrile molecules are coordinated to the Mo centers along the MoMo bond. The absorption wavelength at 507 nm for both 1 and 2 can be assigned to δ_xy→δ_xy* transitions. The solution CD spectra of these two complexes show two prominent bands at 525 and 385 nm and form mirror images of each other. The solid CD spectra of complexes 1 and 2 show marked red-shift in the absorption energies as compared with those measured in solution. The one-electron static coupling mechanism was invoked to explain the CD spectra for these complexes and the second lowest energy bands were assigned to be δ_xy→δ_x²−y² transitions.     

Syntheses and structures of Group 12 metal thioacetate anions, [M(SC{O}Me)nCl4−n] (n=3 and 4) and [Cd2Cl2(SC{O}Me)4]

We have utilized the possibility of altering the ratio of reactants to result in tetrahedral anions, [M(SC{O}Me)_nCl_4−n]²⁻ (n=3, 4) and [Cd₂Cl₂(SC{O}Me)₄]²⁻. Complexes of the formula [Ph₄P]₂[M(SC{O}Me)₄] (M=Zn(II) (1), Cd(II) (2) or Hg(II) (3)) were synthesized by the reaction of thioacetate ligand with the metal salts and Ph₄PCl in 4:1:2 molar ratio in suitable solvents. The geometry of Zn(II) in 1 is nearly tetrahedral and the distortion in tetrahedron increases in the order of 1<2<3 as observed from the SMS angles in the crystal structures. The tendency of monoanionic complexes [Ph₄P][M(SC{O}Me)₃] to react with 1 mole equivalent of Ph₄PCl resulted in complexes of the type [Ph₄P]₂[M(SC{O}Me)₃Cl] (M=Cd(II) (4) or Hg(II) (5)). In the structures of 4 and 5, three sulfur atoms and one chloride atom occupy the corners of the tetrahedron around the metal centers. However, in a 4:2:2 or 2:1:2 molar reaction of Me{O}CS⁻ with CdCl₂ and Ph₄PCl in aqueous medium resulted in a chloro bridged dimer, [Ph₄P]₂[Cd₂(μ-Cl)₂(SC{O}Me)₄] (6) as determined by X-ray crystallography.     

Synthesis and structural characterization of gold(III) dioximates with anions [AuCl4] and [AuCl2]

Two complexes of Au(III) with dimethylglyoxime of compositions [Au^III(HDMG)₂][Au^IIICl₄] (1) and [Au^III(HDMG)₂][Au^ICl₂] (2) were synthesized and characterized by X-ray structural analysis. It was shown that in [Au^III(HDMG)₂]⁺ cation Au(III) has a square-planar environment, and the oxygen atoms of oxime groups are joined by intramolecular H-bond. The secondary Au?Au and Au?Cl interactions in the crystal are discussed.     

Syntheses, characterization and crystal structures of copper(I) o-(diphenylphosphino)benzaldehyde complexes

The complexes [Cu(PCHO)₂(NCMe)][BF₄] (1) and [Cu(PCHO)₃][BF₄] (2) have been prepared by treating [Cu(NCMe)₄][BF₄] with two and three equivalents of Ph₂P(o-C₆H₄)C(O)H (abbreviated as PCHO) at room temperature, respectively. The reaction of 1 and (Ph₂PC₅H₄)₂Fe (abbreviated as DPPF) affords [Cu(PCHO)(DPPF)][BF₄] (3). The molecular structures of 1-3 have been determined by an X-ray diffraction study. The aldehyde groups in 1 are pendant, while one of the formyl groups in 2 is weakly coordinated to the copper ion through the oxygen atom. On the other hand, the copper atom in 3 is strongly chelated by both DPPF and PCHO ligands.     

Syntheses and characterization of luminescent dinuclear and polynuclear Cu(I) complexes containing 4,4′-bis(diphenylphosphino)biphenylene bridge

The dinuclear complex [Cu₂(dpbp)₂(NCMe)₄][BF₄]₂ (1) has been prepared by treating [Cu(NCMe)₄][BF₄] with 4,4′-bis(diphenylphosphino)biphenylene (abbreviated as dpbp). Reactions of 1 with 2,2′-bipyridine and 1,1′-bis(diphenylphosphino)ferrocene (abbreviated as dppf) afford [Cu₂(dpbp)₂(2,2′-bipy)₂][BF₄]₂ (2) and [Cu₂(dpbp)(dppf)₂][BF₄]₂ (3), respectively. In contrast, compound 1 reacts with tetra(2-pyridyl)ethyl-1,4-diaminobutane (abbreviated as tpyda) to produce the polymeric complex {[Cu₂(dpbp)(tpyda)][BF₄]₂}_n (4). Compounds 1-4 are photoluminescent with the emission band (λ_max) in the range 510-554 nm. The crystal structures of 1 and 4 have been determined by an X-ray diffraction study.     

Syntheses and structural characterization of dicopper(I) bis(diphenylphosphino)acetylene complexes containing tricyclic, cyclic and linear frameworks

The complexes [Cu₂(dppa)₃(CH₃CN)₂][BF₄]₂ (1) and Cu₂(dppa)₃(O₃SCF₃)₂ (2) have been prepared in good yields by treating [Cu(MeCN)₄][BF₄] and [Cu(MeCN)₄][O₃SCF₃], respectively, with Ph₂PCCPPh₂ (abbreviated as dppa) at room temperature. The reaction of 1 with di-2-pyridyl ketone (abbreviated as dpyk) produces [Cu₂(dppa)₂(dpyk)₂][BF₄]₂ (3), and with 1,1′-bis(diphenylphosphino)ferrocene (abbreviated as dppf) produces [Cu₂(dppa)(dppf)₂][BF₄]₂ (4). The molecular structures of 1-4 have been determined by an X-ray diffraction study. Compounds 1 and 2 form a helical Cu₂(dppa)₃ metallatricycle, compounds 3 forms a Cu₂(dppa)₂ metallacycle, and compound 4 contains a linear Cu₂(dppa) skeleton.     

Pyridine and phosphine reactions with [CPh3][B(C6F5)4]

Trityl borate salts [4-RPyCPh₃][B(C₆F₅)₄] (R = H 1, ^tBu 2, Et 3, NMe₂4) and [R₃PCPh₃][B(C₆F₅)₄] (R = Me 5, ⁿBu 6, Ph[1] 7, p-MeC₆H₄8) are readily prepared via equimolar reaction of the appropriate pyridine or phosphine and trityl borate [CPh₃][B(C₆F₅)₄]. The analogous reactions of PⁱPr₃ affords the product [(p-ⁱPr₃P-C₆H₄)Ph₂CH][B(C₆F₅)₄] (9) while the corresponding reactions of Cy₃P and ^tBu₃P gave the cyclohexadienyl derivatives [(p-R₃PC₆H₅)CPh₂][B(C₆F₅)₄] (R = Cy 10, ^tBu 11). X-ray structures of 5 and 9 are reported.     

Bimetallic sheet and 3D threefold interpenetrating diamond-like network constructed by chelate Cu cations and Mn dicyanamide polymeric chains. Synthesis, crystal structure, and magnetism of [Cu(L)2][Mn(dca)4] (L=ethylenediamine or 1,3-diaminopropane; dca=dicyanamide N(CN)2)

Two novel bimetallic coordination polymers, [Cu(en)₂][Mn(dca)₄] (1) and [Cu(pn)₂][Mn(dca)₄] (2) (en, ethylenediamine; pn, 1,3-diaminopropane; dca, dicyanamide N(CN)₂⁻), have been synthesized and characterized. Both of them consist of Mndca anionic chains and chelate cations of copper. 1 has a sheet like architecture built by the [Cu(en)₂]²⁺ cations and the homoleptic trans-[Mn(dca)₄ ²⁻]_n chains. 2 shows unusual 3-D threefold interpenetrating diamond-like structure constructed by [Cu(pn)₂]²⁺ cations and the homoleptic cis-[Mn(dca)₄ ²⁻]_n chains. The magnetic susceptibilities obey the Curie-Weiss law with weak antiferromagnetic interactions.     

[Co{Ph2P(O)CH2P(O)Ph2}3][CoCl4] · 8CHCl3: Crystal structure and formation from [Co2(Ph2PCH2PPh2)(CO)6] in chloroform

When a solution of [Co₂(Ph₂PCH₂PPh₂)(CO)₆] in chloroform or deuterochloroform is allowed to stand in air at room temperature, it deposits dark green crystals of [Co{Ph₂P(O)CH₂P(O)Ph₂}₃][CoCl₄] · 8CHCl₃. The same product is formed more quickly and in much higher yield (80% based on Co) if the reaction is carried out in the presence of 2 equiv. of [Ph₂PCH₂PPh₂]; the Co^II appears to catalyse the air-oxidation of [Ph₂PCH₂PPh₂]. The salt was characterised by X-ray crystallography and shown to contain octahedral Co^II cations and Co^II tetrahedral anions having normal bond lengths and angles.     

Preparation of novel (Z)-4-ylidenebenzo[b]furo[3,2-d][1,3]oxazines and their biological activity

A reaction of 2-acetyl-3-acylaminobenzo[b]furans (9d–o) with Vilsmeier (VM) reagent afforded a mixture of (E)- and (Z)-{(E)-2-aralkenylbenzo[b]furo[3,2-d][1,3]oxazin-4-ylidene}acetaldehydes (5) with a characteristic exo-formylmethylene group on the oxazine ring. The Z-isomer was more stable than the E-isomer. The Z-isomers ((Z)-5) were reacted with phosphonate reagents under two different conditions to obtain various butadiene derivatives (12) containing benzo[b]furo[3,2-d][1,3]oxazine skeleton. Typical compounds (5 and 12) were evaluated for their anti-osteoclastic bone resorption activity, antagonistic activity for the cysLT1 receptor and growth inhibitory activity for MIA PaCa-2 and MCF-7. Compounds 12f and 12j showed potent anti-osteoclastic bone resorption activity comparable to E₂ (17β-estradiol).     

Synthesis and structural characterization of the mono- and diphosphine-containing diiron propanedithiolate complexes related to [FeFe]-hydrogenases. Biomimetic H2 evolution catalyzed by (mu-PDT)Fe2(CO)4[(Ph2P)2N(n-Pr)

As the new H-cluster models, six diiron propanedithiolate (PDT) complexes with mono- and diphosphine ligands have been prepared and structurally characterized. The monophosphine model complex (μ-PDT)Fe₂(CO)₅[Ph₂PNH(t-Bu)] (1) was prepared by reaction of parent complex (μ-PDT)Fe₂(CO)₆ (A) with 1 equiv of Ph₂PNH(t-Bu) in refluxing xylene, whereas A reacted with 1 equiv of Me₃NO · 2H₂O in MeCN at room temperature followed by 1 equiv of Ph₂PH to give the corresponding monophosphine model complex (μ-PDT)Fe₂(CO)₅(Ph₂PH) (2). Further treatment of 2 with 1 equiv of n-BuLi in THF at −78 °C followed by 1 equiv of CpFe(CO)₂I from −78 °C to room temperature afforded monophosphine model complex (μ-PDT)Fe₂(CO)₅[Ph₂PFe(CO)₂Cp] (3), whereas the diphosphine model complexes (μ-PDT)Fe₂(CO)₄(Ph₂PC₂H₄PPh₂) (4), (μ-PDT)Fe₂(CO)₄[(Ph₂P)₂N(n-Pr)] (5) and (μ-PDT)Fe₂(CO)₄[(Ph₂P)₂N(n-Bu)] (6) were obtained by reactions of A with ca.1 equiv of the corresponding diphosphines in refluxing xylene. All the new model complexes were characterized by elemental analysis, spectroscopy and particularly for 1 and 3-6 by X-ray crystallography. On the basis of electrochemical and spectroelectrochemical studies, model 5 was found to be a catalyst for HOAc proton reduction to H₂, and for this electrocatalytic reaction an ECCE mechanism was proposed.     

Long-range superexchanged magnetic interaction observed in heterometallic complex: {[Fe(Tpms)(CN)3][Mn(H2O)2(DMF)2]} · DMF

A new tri-cyanometalate building block for heterometallic complexes, [PPh₄]₂[Fe^II(Tpms)(CN)₃] (2) (PPh₄ = tetraphenylphosphonium; Tpms = tris(pyrazolyl) methanesulfonate), has been prepared. Using it as a building block, a one-dimensional chain compound, {[Fe^II(Tpms)(CN)₃][Mn^II(H₂O)₂( DMF)₂]} · DMF (3), has been synthesized and structurally characterized. The magnetic properties of 3 correspond to a ferromagnetic chain with weak long-range superexchanged magnetic interaction between the high-spin manganese(II) ions.     

Synthesis and coordination of the bifunctionalized ylides Ph2P(CH2)n(Ph)2PCHCOOMe (n = 1, 2) and ketenylidene Ph2P(CH2)2(Ph)2PCCO to Pd and Pt complexes

In this paper it is reported the synthesis of the phosphonium salts [Ph₂P(CH₂)_n(Ph)₂PCH₂COOMe]Br (n = 1 (1), 2 (2)) and [Ph₂P(CH₂COOMe)(CH₂)_n(Ph)₂PCH₂COOMe]Br₂ (n = 3 (3)) derived from the reactions of the diphosphines dppm, dppe and dppp with methyl bromoacetate. By reaction of the monophosphonium salt of dppm and dppe with the strong base Na[N(SiMe₃)₂] the corresponding carbonyl stabilized ylides Ph₂P(CH₂)_n(Ph)₂PCHCOOMe (n = 1 (4), 2 (5)) were obtained. The Ph₂P(CH₂)₂(Ph)₂PCHCOOMe (5) ylide was reacted with Pd(II) and Pt(II) substrates. From these reactions were isolated exclusively complexes in which the ylide was chelated to the metal through the free phosphine group and the ylidic carbon atom. A further reaction of the Ph₂P(CH₂)₂(Ph)₂PCHCOOMe (5) ylide with 1.5 equiv. of Na[N(SiMe₃)₂] gives the bifunctionalized ketenylidene Ph₂P(CH₂)₂(Ph)₂PCCO (6) system. This cumulenic ylide reacts with Pt(II) complexes to form a chelated derivative in which IR and NMR spectra suggest the breaking of the CC bond of the -CCO group.     

Crystal structure, magnetic properties and Mössbauer studies of [Fe(qsal)2][Ni(dmit)2]

A new compound of formula [Fe(qsal)₂][Ni(dmit)₂] (1) has been synthesised, structurally and magnetically characterised (qsalH = N-(8-quinolyl)salicylaldimine, dmit²⁻ = 1,3-dithiol-2-thione-4,5-dithiolato). Its structural features and its magnetic behaviour were compared with those of [Fe(qsal)₂]-based complexes, and more particularly [Fe(qsal)₂][Ni(dmit)₂] · 2CH₃CN.     

Synthesis and antitubercular evaluation of amidoalkyl dibenzofuranols and 1H-benzo[2,3]benzofuro[4,5-e][1,3]oxazin-3(2H)-ones

A new class of amidoalkyl dibenzofuranols and 1H-benzo[2,3]benzofuro[4,5-e][1,3]oxazin-3(2H)-ones was synthesized in very good yields through polyphosphoric acid supported on silica (PPA-SiO₂) catalyzed one-pot three component condensation of 2-dibenzofuranol; aromatic aldehydes and acetamide or benzamide or urea under solvent free conditions. At 125 °C the reaction led to the formation of amidoalkyl dibenzofuranols 5a-k where as at 160 °C cyclization take place to give oxazin-3(2H)-one analogues 6a-e. Screening all the 16 compounds for in vitro antimycobacterial activity against Mycobacterium tuberculosis H37Rv (MTB) resulted 1-((4-chlorophenyl)(2-hydroxydibenzo[b,d]furanyl)methyl)urea 5h; 1-((4-bromophenyl)(2-hydroxydibenzo[b,d]furanyl)methyl)urea 5i; 1-phenyl-1H-benzo[2,3]benzo furo[4,5-e][1,3]oxazin-3(2H)-one 6a (MIC 3.13 μg/mL) and 1-(4-chlorophenyl)-1H-benzo[2,3]benzofuro[4,5-e][1,3]oxazin-3(2H)-one 6b; 1-(4-bromophenyl)-1H-benzo[2,3]benzofuro [4,5-e][1,3]oxazin-3(2H)-one 6c (MIC 1.56 μg/mL) as most active antitubercular agents.     

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.     

The influence of substituents (R) at N atom of thiophene-2-carbaldehyde thiosemicarbazones {(C4H3S)HCN-N(H)-C(S)NHR} on bonding, nuclearity and H-bonded networks of copper(I) complexes

The nuclearity, bonding and H-bonded networks of copper(I) halide complexes with thiophene-2-carbaldehyde thiosemicarbazones {(C₄H₃S)HC²N³-N(H)-C¹(S)N¹HR} are influenced by R substituents at N¹ atom. Thiophene-2-carbaldehyde-N¹-methyl thiosemicarbazone (HttscMe) or thiophene-2-carbaldehyde-N¹-ethyl thiosemicarbazone (HttscEt) have yielded halogen-bridged dinuclear complexes, [Cu₂(μ-X)₂(η¹-S-Htsc)₂(Ph₃P)₂] (Htsc, X: HttscMe, I, 1; Br, 2; Cl, 3; HttscEt, I, 4; Br, 5; Cl, 6), while thiophene-2-carbaldehyde-N¹-phenyl thiosemicarbazone (HttscPh) has yielded mononuclear complexes, [CuX(η¹-S-HttscPh)₂] (X, I, 7a; Br 8; Cl, 9) and a sulfur bridged dinuclear complex, [Cu₂(μ-S-HttscPh)₂(η¹-S-HttscPh)₂I₂] 7b co-existing with 7a in the same unit cell. These results are in contrast to S-bridged dimers [Cu₂(μ-S-Httsc)₂(η¹-Br)₂(Ph₃P)₂] · 2H₂O and [Cu₂(μ-S-Httsc)₂(η¹-Cl)₂(Ph₃P)₂] · 2CH₃CN obtained for R = H and X = Cl, Br (Httsc = thiophene-2-carbaldehyde thiosemicarbazone) as reported earlier. The intermolecular CH_Ph?π interaction in 1-3 (2.797 Å, 1; 3.264 Å, 2; 3.257 Å, 3) have formed linear polymers, whereas the CH_Ph?X and N³?HCH interactions in 4-6 (2.791, 2.69 Å, 5; 2.776, 2.745 Å, 6, respectively) have led to the formation of H-bonded 2D polymer. The PhN¹H?π, interactions (2.547 Å, 8, 2.599 Å, 9) have formed H-bonded dimers only. The Cu?Cu separations are 3.221-3.404 Å (1-6).     

Sn-S and Ru-Ru bonds cleavage reactions between [Ph3SnS(CH2)3SSnPh3] and Ru3(CO)12: X-ray crystal structures of [Ph3SnS(CH2)3SSnPh3] and trans-[Ru(CO)4(SnPh3)2]

The organotin complex [Ph₃SnS(CH₂)₃SSnPh₃] (1) was synthesized by PdCl₂ catalyzed reaction between Ph₃SnCl and disodium-1,3-propanedithiolate which in turn was prepared from 1,2-propanedithiol and sodium in refluxing THF. Reaction of 1 with Ru₃(CO)₁₂ in refluxing THF affords the mononuclear complex trans-[Ru(CO)₄(SnPh₃)₂] (2) and the dinuclear complex [Ru₂(CO)₆(μ-κ²-SCH₂CH₂CH₂S)] (3) in 20 and 11% yields, respectively, formed by cleavage of Sn-S bond of the ligand and Ru-Ru bonds of the cluster. Treatment of pymSSnPPh₃ (pymS = pyrimidine-2-thiolate) with Ru₃(CO)₁₂ at 55-60 °C also gives 2 in 38% yield. Both 1 and 2 have been characterized by a combination of spectroscopic data and single crystal X-ray diffraction analysis.     

Insertion reactions of organic anhydrides and the Cu(I) alkoxide [CuOBu]

The synthesis and structural characterization of the copper salts [Cu₈(benzoate)₈(THF)₆] (1), [Cu₂{(CO₂)₂C₆H₂(Boc)₂}dppm₂]₂ (2) and [Cu₂{(CO₂)₂C₁₀H₄(Boc)₂}dppm₂]₂ (3) [Boc = tert-butoxycarbonyl, dppm = 1,2-bis(diphenylphosphino)methane] prove that cyclic organic anhydrides and dianhydrides readily insert into the Cu-O bond of [CuO^tBu] forming carboxylate ligands with ester functionalities in the ligand periphery. [Mn₃(o-Boc-benzoate)₆(DME)₂] (4) (DME = 1,2-dimethoxyethane) was synthesized by the metathesis reaction of [Cu(I)(o-Boc-benzoate)] with MnCl₂.