The in vitro antifungal activity of some dithiocarbamate organotin(IV) compounds on Candida albicans— a model for biological interaction of organotin complexes

The in vitro antifungal activity of the dithiocarbamate organotin complexes [Sn{S₂CN(CH₂)₄}₂Cl₂] ( 1 ), [Sn{S₂CN(CH₂)₄}₂Ph₂] ( 2 ), [Sn{S₂CN(CH₂)₄}Ph₃] ( 3 ), [Sn{S₂CN(CH₂)₄}₂n‐Bu₂] ( 4 ), [Sn{S₂CN(CH₂)₄}Cy₃] {Cy = cyclohexyl} ( 5 ), [Sn{S₂CN(C₂H₅)₂}₂Cl₂] ( 6 ), [Sn{S₂CN(C₂H₅)₂}₂Ph₂] ( 7 ), [Sn{S₂CN(C₂H₅)₂}Ph₃] ( 8 ), [Sn{S₂CN(C₂H₅)₂}₃Ph] ( 9 ) and [Sn{S₂CN(C₂H₅)₂}Cy₃] ( 10 ) has been screened against Candida albicans (ATCC 18804), Candida tropicalis (ATCC 750) and resistant Candida albicans collected from HIV‐positive Brazilian patients with oral candidiasis. All compounds exhibited antifungal activities and complexes 3 and 8 displayed the best results. We have investigated the effect of compounds 1–10 on the cellular activity of the yeast cultures. Changes in mitochondrial function have not been detected. However, all drugs reduced ergosterol biosynthesis. Preliminary studies on DNA integrity indicated that the compounds do not cause gross damage to yeast DNA. The data suggest that these compounds share some mechanisms of action on cell membranes similar to that of polyene but not with azole drugs, normally used in Candida infections. Copyright © 2008 John Wiley & Sons, Ltd.     

(1,3-Diformylindenyl)cyclopentadienyl ruthenium derivatives

The reaction of [CpRu(CH₃CN)₃][PF₆], [Cp*RuCl] _n , and [Cp^FRuCl]n with 1,3-diformylindene results in the predominant formation of zwitter-ionic arene-cyclopentadienyl complexes {η⁶-1,3-(CHO)₂C₉H₅}RuCp (Cp = C₅H₅), {η⁶-1,3-(CHO)₂C₉H₅}RuCp* (Cp* = C₅Me₅), and {η⁶-1,3-(CHO)₂C₉H₅}RuCp^F (Cp^F = C₅Me₄CF₃), respectively. The ruthenocenes {η⁵-1,3-(CHO)₂C₉H₅}RuCp, {η⁵-1,3-(CHO)₂C₉H₅}RuCp*, and {η⁵-1,3-(CHO)₂C₉H₅}RuCpF were synthesized by the reaction of 1,3-diformylindenyl potassium with [CpRu(CH₃CN)₃][PF₆], [Cp*RuCl] _n , and [Cp^FRuCl] _n .     

General theoretical analysis of three-connected polyhedral molecules and their capped derivatives

The synthesis of the half-sandwich compound Na[(C₅H₅)Ni{P(S)(CH₃)₂}₂] is described. The anions [(C₅H₅)Ni{P(S)R₂}₂]^?, 1a (R = OCH₃) and 1b (R = CH₃) react as bidentate sulfur ligands with [Ni₂(C₅H₅)₃]⁺, giving nickelocene and weakly paramagnetic dinuclear complexes of the type [(C₅H₅)Ni{P(S)R₂}₂Ni(C₅H₅)] (2a,b). In these compounds, the P(S)R₂ units form NiPSNi bridges in such a fashion as to generate a (C₅H₅)NiP₂ and a (C₅H₅)NiS₂ unit. A temperature-dependent singlettriplet spin equilibrium is observed, which is essentially localized on the (C₅H₅)NiS₂ side. Accordingly, the position of the cyclopentadienyl peak of the (C₅H₅)Ni unit bound to the two sulfur donor centers displays a very large temperature dependence in the ¹H NMR spectra. MO model calculations (EHT) for P(S)H₂^?, [(C₅H₅)Ni{P(S)H₂}₂]^? (1c), [(C₅H₅)Ni{P(S)H₂}₂Ni(C₅H₅)] (2c) and its isomer 3c allow the observed spin crossover to be explained as a consequence of the pronounced π-donor properties of the sulfur centers and allow predictions for related complexes.The green complexes 2a,b isomerize completely and irreversibly in a first-order reaction to yield the diamagnetic red compounds [{(C₅H₅)NiP(S)R₂}₂] (3a,b), in which each (C₅H₅)Ni unit is coordinated to one P and one S donor atom. The rate constant of isomerization of 2a, k (7.6 ± 0.3) × 10^?4s^?1 at 306 K, and the energy of activation, E_a 76 kJ mol^?1, have been determined. The rate of isomerization is independent of the solvent, and crossover experiments verify that the isomerization is an intramolecular process without involvement of the monomeric units [(C₅H₅)NiP(S)R₂].     

Reactions of iridium and platinum complexes with N-sulfinyl compounds

The reactions of substituted N-sulfinylanilines with the complexes {Pt[P(C₆H₅₃]₂O₂} and {IrClCO[P(C₆H₅)₃]₂} have been reinvestigated. The former complex yields {Pt[P(C₆H₅)₃]₂SO₄} as the only isolable product in reactions with N-sulfinylaniline. In contrast to a previous report, Vaska's complex has been found not to react with C₆H₅NSO under anhydrous conditions. {Pt[P(C₆H₅)₃]₂-(C₂H₄)} reacts with N-sulfinyl compounds to give complexes of formula {Pt[P(C₆H₅)₃]₂-(RNSO)} where R = C₆H₅, p-O₂NC₆H₄, p-CH₃C₆H₄, or p-CH₃C₆H₄SO₂. {Pt[P(C₆H₅)₃]₃} reacts with C₆H₅NSO to give the same product obtained from reaction with the ethylene complex. Vaska's complex and its bromo analog form 1:1 adducts with p-O₂NC₆H₄NSO.     

Binding forms of gold(III) from solutions by cadmium diethyl dithiocarbamate: Thermal behavior and role of secondary interactions in the supramolecular self-assembly of polymeric complexes ([Au{S2CN(C2H5)2}2][AuCl4]) n and [Au{S2CN(C2H5)2}Cl2] n

The chemisorption interaction between the binuclear cadmium diethyl dithiocarbamate (EDtc), [Cd₂{S₂CN(C₂H₅)₂}₄], (chemisorbent I) and AuCl₃ solutions in 2 M HCl results in the formation of polymeric gold(III) complexes: ([Au{S₂CN(C₂H₅)₂}₂][AuCl₄]) _n (II) and [Au{S₂CN(C₂H₅)₂}Cl₂] _n (III) with the same Au : EDtc : Cl ratio (1 : 1 : 2). The alternating centrosymmetric cations and anions of complex II are structurally self-assembled to form linear polymeric chains: the gold atom in [Au{S₂CN(C₂H₅)₂}₂]⁺ forms secondary Au(1)?Cl(1) bonds (3.7784 Å) with two neighboring [AuCl₄]^? anions. This binding is additionally strengthened by secondary S(1)?Cl(1) interactions (3.4993 Å). The mixed-ligand complex III comprises two structurally non-equivalent molecules [Au{S₂CN(C₂H₅)₂}Cl₂]: A—Au(1) and B—Au(2), each being in contact with two nearest neighbors through pairs of unsymmetrical secondary bonds: Au(1)?S(1)^a/b 3.4361/3.6329; and Au(2)?S(4)^c/d 3.4340/3.6398 Å. At the supramolecular level, this gives rise to independent zigzag-like polymeric chains, (?A?A?A?) _n and (?B?B?B?) _n along which antiparallel isomeric molecules of III alternate. The chemisorption capacity of cadmium diethyl dithiocarbamate calculated from the gold(III) binding reaction is 963.2 mg of gold per 1 g of the sorbent. The recovery conditions for the bound gold were elucidated by simultaneous thermal analysis of II and III. The DSC curves reflect different sets of heat effects, because thermolysis occurs for complex molecules (III) or for cations and anions (II). Nevertheless, the patterns of experimental TG curves are similar despite different structures of the complexes. The final product of thermal transformations is reduced gold.     

Formation of supramolecular complexes in reactions of adduct formation of zinc diethyldithiocarbamate with morpholine. Molecular structures and thermal properties

A supramolecular compound of the general formula [Zn{NH(CH₂)₄O} {S₂CN(C₂H₅)₂}₂]₄ · NH(CH₂)₄O · C₂H₄{N(CH₂)₄O}₂ (I) was obtained and examined by X-ray diffraction analysis and thermography. According to X-ray diffraction data, the crystal lattice of compound I shows an unusual alternation of two independent centrosymmetric supramolecular complexes [Zn{NH(CH₂)₄O} {S₂CN(C₂H₅)₂}₂]₂ · C₂H₄{N(CH₂)₄O}₂ (Ia) and [Zn{NH(CH₂)₄O} {S₂CN(C₂H₅)₂}₂]₂ · NH(CH₂)₄O (Ib). Either complex includes two molecules of an adduct of bis(diethyldithiocarbamato)zinc with morpholine and outer-sphere molecules of 1,2-dimorpholinoethane or morpholine. Adduct molecules are structurally nonequivalent in pairs and linked with solvate molecules by hydrogen bonds. The calculated geometries of the zinc polyhedra are intermediate between trigonal bipyramid and tetragonal pyramid. Thermal decomposition of supramolecular compound I proceeds through desorption of the outer-sphere and coordinated organic molecules; in the final step, defragmentation of the dithiocarbamate part gives zinc sulfide.     

A ferrocenyl-bridged intramolecularly coordinated bis(diorganostannylene): Synthesis, molecular structure and reactivity of [4-t-Bu-2,6-{P(O)(O-i-Pr)2C6H2Sn}C5H4]2Fe

The intramolecularly coordinated heteroleptic stannylene [4-t-Bu-2,6-{P(O)(O-i-Pr)₂}₂C₆H₂]SnCl serves as synthon for the synthesis of the ferrocenyl-bridged bis(diorganostannylene) [4-t-Bu-2,6-{P(O)(O-i-Pr)₂}₂C₆H₂SnC₅H₄]₂Fe (1) which in turn reacts with W(CO)₆ and Cr(CO)₄(C₇H₈) to provide the corresponding transition metal complexes [4-t-Bu-2,6-{P(O)(O-i-Pr)₂}₂C₆H₂Sn{W(CO)₅}C₅H₄]₂Fe (2) and [4-t-Bu-2,6-{P(O)(O-i-Pr)₂}₂C₆H₂SnC₅H₄]₂Fe · Cr(CO)₄ (3), respectively. Reaction of compound 1 with sulphur and atmospheric moisture gave, under partial tin-carbon and oxygen-carbon bond cleavage, a tetranuclear organotin-oxothio cluster 5. All compounds were characterized by ¹H, ¹³C, ³¹P, and ¹¹⁹Sn NMR, and IR spectroscopy, as well as by single-crystal X-ray diffraction analysis. Compounds 1 and 3 were also investigated by Mössbauer spectroscopy. Cyclovoltametric studies reveal the influence of the organostannyl moieties on the redox-behaviour of compounds 1-3 in comparison with unsubstituted ferrocene.     

Bis­[bis(N,N‐diethyl‐1,1‐di­seleno­car­bam­ato)copper(II)], [Cu(Se2CNEt2)2]2

The title centrosymmetric Cu^II binuclear complex, bis(μ‐N,N‐diethyl‐1,1‐di­seleno­carbamato‐Se,Se′:Se)­bis­[(N,N‐diethyl‐1,1‐di­seleno­carbamato‐Se,Se′)copper(II)], [Cu(Se₂CNEt₂)₂]₂ or [Cu₂(C₅H₁₀NSe₂)₄], is built from two symmetry‐related [Cu{Se₂CN(Et)₂}₂] units by pairs of Cu—Se bonds. The coordination geometry at the unique Cu atom is distorted square pyramidal, with Cu—Se distances in the range 2.4091 (11)—2.9095 (10) Å.     

A family of three-dimensional porous coordination polymers with general formula (Kat)2[{M(H2O)n}3{Re6Q8(CN)6}2]·xH2O (Q=S, Se; n=1.5, 2)

The X-ray crystal structures of a series of new compounds (H₃O)₂[{Mn(H₂O)_1.5}₃{Re₆Se₈(CN)₆}₂]·19H₂O (1), (Me₄N)₂[{Co(H₂O)_1.5}₃{Re₆S₈(CN)₆}₂]·13H₂O (2), (Me₄N)₂[{Co(H₂O)_1.5}₃{Re₆Se₈(CN)₆}₂]·3H₂O (3), (Et₄N)₂[{Mn(H₂O)₂}₃{Re₆Se₈(CN)₆}₂]·6.5H₂O (4), (Et₄N)₂[{Ni(H₂O)₂}₃{Re₆S₈(CN)₆}₂]·6.5H₂O (5), and (Et₄N)₂[{Co(H₂O)₂}₃{Re₆S₈(CN)₆}₂]·10H₂O (6) are reported. All six compounds are isostructural crystallizing in cubic space group with four formulae per unit cell. For compounds 1, 3-5 the following parameters were found: (1) a=19.857(2) Å, R1=0.0283; (3 at 150 K) a=19.634(1) Å, R1=0.0572; (4) a=20.060(2) Å, R1=0.0288; (5) a=19.697(2) Å, R1=0.0224. The structures consist three-dimensional cyano-bridged framework formed by cyano cluster anions [Re₆Q₈(CN)₆]⁴⁻, Q=S, Se and transition metal cations, M²⁺=Mn²⁺, Co²⁺, Ni²⁺. Water molecules and large organic cations Me₄N⁺ and Et₄N⁺ are included in cavities of this framework. Porosity of the framework, its ability to accommodate different cations and water molecules by little changes in the structure, as well as distortion of coordination framework under loss of water of crystallization is discussed.     

A new cyanobridged one-dimensional coordination polymer based on the octahedral rhenium cluster [Re6Se8(CN)6]4−: Synthesis and crystal structure of [{Cu(H2O)0.5(en)2} {Cu(en)2}Re6Se8(CN)6]·3H2O

The rhenium cluster complex [{Cu(H₂O)_0.5(en)₂} {Cu(en)₂} Re₆Se₈(CN)₆]·3H₂O has been obtained by the reaction of an aqueous solution of K₄[Re₆Se₈(CN)₆]·3.5H₂O with an aqueous solution of Cu(en)₂Cl₂ using cross diffusion through a gel. The structure of the compound has been characterized by a single-crystal X-ray diffraction method (a = 10.690(3) Å, b = 15.035(5) Å, c = 25.847(8) Å, V = 4154(2) ų, Z = 4, space group P2₁2₁2₁, R = 0.0651). Cluster anions [Re₆Se₈(CN)₆]^4? in the complex are connected with Cu²⁺ cations by cyano bridges resulting in zigzag chains. Coordination environment of cations is completed by ethylenediamine molecules. Additionally each cluster anion is coordinated by one terminal fragment {Cu(H₂O)_0.5(en)₂}.     

Synthesis and structural characterization of the first trialkylguanidinate and hexahydropyramidopyramidinate complexes of tin

The first guanidinate complexes of tin have been prepared using N,N′,N′′-trialkylguanidinates ([(RN)₂C(NRH)]⁻; R=cyclohexyl; isopropyl) and 1,3,4,6,7,8-hexahydro-2H-pyramido[1,2-a]pyramidinate (hpp⁻) as ligands. The direct reaction between triisopropylguanidine and SnCl₄ provided the complex {[ⁱPrN]₂C[NHⁱPr]}SnCl₃ (1) along with concomitant formation of the guanidinium salt {C[NHⁱPr]₃}⁺[SnCl₅(THF)]⁻ (2). The Sn(II) guanidinate complexes {(C₆H₁₁N)₂C[NH(C₆H₁₁)]}₂Sn (3) and {CN[N(CH₂)₃]₂}₂Sn (4) were prepared through metathesis reactions between 0.5 equiv. SnCl₂ and (C₆H₁₁N)₂C[NH(C₆H₁₁)]Li or hppLi, respectively. Complex 4 is the first reported mononuclear complex of this ligand. In contrast, the reaction of hppLi with 1 equiv. SnCl₂ afforded a bridging dinuclear species, {CN[N(CH₂)₃]₂SnCl}₂ (5). A second mononuclear complex of the hpp⁻ ligand, {CN[N(CH₂)₃]₂}₂SnCl₂ (6), was the product obtained from the reaction of 2 equiv. of hppLi with SnCl₄. The full structural details of compounds 1 and 3–6 are reported. In the case of compounds 1 and 3 these results revealed a distinctly unsymmetrical bonding mode for the bidentate guanidinate ligand and suggest variable degrees of π delocalization with the ligand. The geometries of the Sn centers in 3, 4 are derived from distorted trigonal bipyramidal coordination with a stereochemically active lone pair occupying one coordination site. In contrast, complex 5 displayed a geometry derived from a tetrahedral ligand array with one vertex occupied by a lone pair of electrons. Complex 6 is six coordinate and possesses 2 equiv. chelating bidentate hpp⁻ ligands and two cis-chloro groups.     

Organoselenium compounds containing pyrazole or phenylthiazole groups: Synthesis,structure, tin(IV) complexes and antiproliferative activity

The diorganodiselenides (pzCH₂CH₂)₂Se₂ ( 1 ) and (PhtzCH₂)₂Se₂ ( 2 ) were prepared by reacting Na₂Se₂ with 1‐(2‐bromoethyl)‐1H‐pyrazole and 4‐(chloromethyl)‐2‐phenylthiazole, respectively, while the reactions between 1‐(2‐bromoethyl)‐1H‐pyrazole or 4‐(chloromethyl)‐2‐phenylthiazole and the lithium organoselenolates [2‐(Et₂NCH₂)C₆H₄]SeLi and [2‐{O(CH₂CH₂)₂NCH₂}C₆H₄]SeLi in a 1:1 molar ratio resulted in the heteroleptic diorganoselenium(II) compounds [2‐(Et₂NCH₂)C₆H₄](R)Se (R = pzCH₂CH₂ ( 3 ) or PhtzCH₂ ( 5 )) and [2‐{O(CH₂CH₂)₂NCH₂}C₆H₄](R)Se (R = pzCH₂CH₂ ( 4 ) or PhtzCH₂ ( 6 )). The diorganotin(IV) bis(organoselenolato) derivatives of type R₂Sn(SeCH₂CH₂pz)₂ (R = 2‐(Me₂NCH₂)C₆H₄ ( 7 ) or Me ( 8 )) were obtained by reacting (pzCH₂CH₂)SeNa with the appropriate diorganotin(IV)dichloride in a 2:1 molar ratio. All compounds were investigated using NMR spectroscopy (¹H, ¹³C, ⁷⁷Se, ¹¹⁹Sn as appropriate) and ESI+ mass spectrometry. The molecular structures of 2 and 6 were determined using single‐crystal X‐ray diffraction. The formation of a 10–Se–3 hypercoordinated species was evidenced for 6 in the solid state, as a consequence of the C,N coordination behaviour of the 2‐{O(CH₂CH₂)₂NCH₂}C₆H₄ group. Compounds 1 , 7 and 8 were investigated for their antiproliferative activity towards the mouse colon carcinoma C26 cell line with the preliminary results showing a better activity than 5‐fluorouracil.     

Synthesis,and characterization of some Cu(I) complexes having propionitrile and pyridine moieties: An investigation on their antibacterial properties

The aim of producing new biologically active compounds lead to the synthesis of some Cu(I) complexes of general formula [Cu(C₂H₅CN)₄][A] and [Cu(C₅H₅N)₄][A] (1–4) {where A: counter anion = B(C₆F₅)₄⁻ and B{C₆H₃(m-CF₃)₂}₄⁻} from the reaction of CuCl and silver salt of the corresponding counter anion. The complexes were characterized using elemental analysis, ¹H NMR, ¹¹B NMR, FT-IR Spectroscopy, UV–visible spectroscopy and thermo-gravimetric analysis (TGA). The antibacterial activities of all complexes are evaluated by the minimal inhibitory concentration (MIC), using the micro-broth dilution method, against eight bacteria (Gram-negative and Gram-positive), each with fresh clinical isolates. The MIC results were compared with those of Oxytetracycline agent as a positive control. In most cases, the compounds show broad-spectrum activities that were either, more active, or equipotent to, the antibiotic agent in the comparison tests. Complex 4 showed the greatest activity against Proteus mirabilis (Gram- negative) with a minimum inhibitory concentration (MIC) of 8 µg/mL, while complexes 2 and 3 showed the lowest activity against Pseudomonas aeruginosa (Gram-negative) and against Staphylococcus aureus (Gram-positive) with a concentration of 512 µg/mL.     

Phase equilibria in the PbSe-Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript>-Se system and thermodynamic properties of intermediate phases

The Pb-Bi-Se system in the PbSe-Bi₂Se₃-Se-Se composition region was studied by measurement of concentration circuits of the type (−) PbSe(solid) liquid electrolyte, Pb²⁺(Pb-Bi-Se)(solid) (+) in the temperature range 300–430 K and by X-ray powder diffraction. A solid-phase equilibrium diagram was constructed, and the formation was confirmed for the ternary compounds Pb₅Bi₆Se₁₄, Pb₅Bi₁₂Se₂₃, and Pb₅Bi₁₈Se₃₂, which belong to the homologous series [(PbSe)₅] _m · [(Bi₂Se₃)₃] _n . From the emf versus temperature equations, the partial thermodynamic functions [`(DG)]\overline {\Delta G}, [`(DH)]\overline {\Delta H}, [`(DS)]\overline {\Delta S} of PbSe in alloys were calculated. Based on the solid-phase equilibrium diagram from these partial molar quantities using the corresponding data for PbSe and Bi₂Se₃, the standard thermodynamic functions of formation and standard entropies of the above ternary compounds were calculated.     

First examples of cyano-bridged complexes based on a novel cluster anion [Re<Subscript>12</Subscript>C<Subscript>17</Subscript>(CN)<Subscript>6</Subscript>]<Superscript>6−</Superscript>

Two cyano-bridged compounds of novel dodecanuclear cluster anion [Re₁₂CS₁₇(CN)₆] with Ni²⁺ cations were synthesized, namely, one-dimensional polymer of the composition [{Ni(NH₃)₄} {Ni(NH₃)₅}₂Re₁₂CS₁₇(CN)₆] · 7H₂O (I) with a chain structure and [Ni(NH₃)₆]₃[{Ni(NH₃)₄}₃ {Re₁₂CS₁₇(CN)₆}₂] · 21H₂O (II), containing the anionic dimeric complex [{Ni(NH₃)₄}₃ {Re₁₂CS₁₇(CN)₆}₂]^6?. The structures of both compounds were established by X-ray diffraction analysis. Crystals I are monoclinic, space group P2/n, a = 15.321(3), b = 12.635(2), c = 15.448(3) Å, β = 100.242(3)°, V = 2942.8(8) ų, Z = 2. Crystals II are trigonal, space group R3, a = b = 19.7987(14), c = 28.8642(18) Å, V = 9798.6(12) ų, Z = 3.     

Structural organization of dithiocarbamate heteropolynuclear gold(III)-cadmium complexes from X-ray crystallography and 113Cd MAS NMR spectroscopy data

We study the interaction of dialkyl substituted and cyclic cadmium dithiocarbamates with [AuCl₄]^? anions in 2M HCl medium. The state of the chemisorbents upon contact with AuCl₃ solutions is controlled by ¹¹³Cd MAS NMR spectroscopy. The result of the heterogeneous reactions involving chemisorption binding of gold(III) from the solutions and partial ion exchange is the formation of heteropolynuclear gold(III)-cadmium complexes. The crystal and molecular structure of the acetone-solvated form of polymeric bis-(N,N-diethyldithiocarbamato-S,S′) gold(III) hexachlorodicadmate is identified by single-crystal XRD. The main structural moieties of the compound are complex [Au{S₂CN(C₂H₅)₂}₂]⁺ cations and [Cd₂Cl₆]^2? anions. The structural self-organization of the complex at the supramolecular level is attributed to the secondary Au…S bonds between neighboring isomeric complex gold(III) cations; the bonding results in the formation of linear polymer ([Au{S₂CN(C₂H₅)₂}₂]⁺) _n chains, with [Cd₂Cl₆]^2? anions alternating to the right and left of the chains.     

P,C,P-Pincer complexes of ruthenium based on ruthenocene and pentamethylruthenocene

The first ruthenocene- and pentamethylruthenocene-based ruthenium pincer complexes, RuCl(CO)[{2,5-(Bu^t ₂PCH₂)₂C₅H₂}Ru(C₅H₅)] and RuCl(CO)[{2,5-(Bu^t ₂PCH₂)₂C₅H₂}Ru-(C₅Me₅)], were synthesized by cyclometallation of {1,3-(Bu^t ₂PCH₂)₂C₅H₂}Ru(C₅H₅) and {1,3-(Bu^t ₂PCH₂)₂C₅H₂}Ru(C₅Me₅), respectively, with RuCl₂(DMSO)₄ in 2-methoxyethanol and characterized by ¹H and ³¹P{¹H} NMR spectroscopy, and X-ray diffraction.     

Reduction of (1,3-diformylindenyl)cyclopentadienylruthenium derivatives

The reduction of the (1,3-diformylindenyl)cyclopentadienylruthenium derivatives {η⁵-1,3-(CHO)₂C₉H₅}RuCp (Cp = C₅H₅), {η⁵-1,3-(CHO)₂C₉H₅}RuCp* (Cp* = C₅Me₅), and {η⁵-1,3-(CHO)₂C₉H₅}RuCpF (Cp^F = C₅Me₄CF₃) with NaBH₄ or LiAlH₄ under mild conditions affords the [1,3-bis(hydroxymethyl)indenyl]cyclopentadienylruthenium complexes {η⁵-1,3-(CH₂OH)₂C₉H₅}RuCp, {η⁵-1,3-(CH₂OH)₂C₉H₅}RuCp*, and {η⁵-1,3-(CH₂OH)₂C₉H₅}-RuCp^F, respectively, in good yields.     

Substituted Ferrocenylboranes – Potential Ligand Precursors for ansa‐ Metallocenes,Constrained Geometry Complexes and ansa‐Diamido Complexes

A wide range of potential ligand precursors and related compounds have been synthesized from ferrocenyldibromoborane and ferrocenylenebis(dibromoborane) via salt elimination reactions. These comprise ligand precursors suitable for the preparation of (i) ansa‐metallocenes such as [FcB(η¹‐C₅H₅)₂] ( 2 ), [FcB(1‐C₉H₇)₂] ( 3 ), [FcB(3‐C₉H₇)₂] ( 4 ) and [1,1′‐fc{B(3‐C₉H₇)₂}₂] ( 11 ), (ii) constrained geometry complexes such as [FcB(1‐C₉H₇)N(H)Ph] ( 7 ) and [FcB(3‐C₉H₇)N(H)Ph] ( 8 ), (iii) ansa‐diamido complexes such as [FcB(N(H)Ph)₂] ( 9 ) as well as (iv) the related compounds [FcB(Br)N(H)tBu] ( 5 ), [FcB(Br)N(H)Ph] ( 6 ), [1,1′‐fc{B(Br)N(SiMe₃)₂}₂] ( 12 ) and [1,1′‐fc{B(Br)NiPr₂}₂] ( 13 ) (Fc = ferrocenyl, fc = ferrocenylene, C₅H₅ = cyclopentadienyl, C₉H₇ = indenyl). All new compounds have been characterised by multinuclear NMR spectroscopic techniques and in the case of 7 and 12 by X‐ray diffraction methods.     

Framework polymers based on octahedral chalcocyanide cluster [Re6Q8(CN)6]4−/3− anions (Q = Se, Te) and [Nd(Bipy)n]3+ Complexes (n = 1, 2)

Interaction of salts of the cluster anions {Re [Re₆Q₈(CN)₆]^4?/3? (Q = Se, Te) with Nd salts in the presence of 2,2′-bipyridyl (Bipy) ligand brings about new coordination polymers: Pr ₄ ⁿ N[{Nd(Bipy)(H₂O)₄} {Re₆Se₈(CN)₆}] · 2H₂O (I) (space group C2/c, a = 18.2918(16) Å, b = 14.9972(13) Å, c = 37.513(3) Å, β = 102.046(4)°, V = 10064.2(15) ų, Z = 8), [{Nd(Bipy)₂(H₂O)} {Re₆Se₈(CN)₆}] (II) (space group C2/c, a = 15.8668(3) Å, b = 13.5403(3) Å, c = 20.5189(4) Å, β = 110.135(1)°, V = 4138.89(15) Å₃, Z = 4), and [{Nd(Bipy)(EtOH)(H₂O)₄}{Re₆Te₈(CN)₆}] · EtOH (III) (space group $P\bar 1$ , a = 9.4733(6) Å, b = 12.5326(8) Å, c = 17.2374(11) Å, α = 96.561(2)°, β = 90.310(2)°, γ = 94.876(2)°, V = 4138.89(15) Å₃, Z = 4). The compounds synthesized are characterized by single-crystal X-ray diffraction and IR methods. Compounds I and III have layered (2D) structures, compound II is a framework (3D) polymer.