Search

An AgI dimer capped with labile organometallic diphosphorus ligands [Cp2Mo2(CO)4(η2‐P2)] (Cp=C5H5) acts as a highly pre‐organized molecular precursor to direct the construction of 1D or 2D, and 3D organometallic–organic hybrid coordination polymers upon reaction with ditopic pyridine‐based linkers. The formation of the supramolecular aggregates can be controlled by the stoichiometry of the organic molecules, and the mechanism is supported by DFT calculations.

A detailed method for the preparation of [Cp''2 Zr(η1:1 -P4 )] (1) is presented. The coordination behavior of 1 towards Lewis acidic transition metal complexes of tungsten, manganese, and iron, respectively, and main group compounds (AlMe3 , AlEt3 ) was investigated in detail by computational and experimental studies. In doing so, a series of unprecedented complexes with different coordination modes and multiple coordination numbers of the tetraphosphabicyclo[1.1.0]butane framework were synthesized. All products, as well as the starting materials, were comprehensively characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single crystal X-ray structural analysis.

The cyclo-P4 complexes [CpRTa(CO)2(η4-P4)] (CpR: Cp′′=1,3-C5H3tBu2, Cp′′′=1,2,4-C5H2tBu3) turned out to be predestined for the formation of hollow spherical supramolecules with non-classical fullerene-like topology. The resulting assemblies constructed with CuX (X=Cl, Br) showed a highly symmetric 32-vertex core of solely four- and six-membered rings. In some supramolecules, the inner cavity was occupied by an additional CuX unit. On the other hand, using CuI, two different supramolecules with either peanut- or pear-like shapes and outer diameters in the range of 2–2.5 nm were isolated. Furthermore, the spherical supramolecules containing Cp′′′ ligands at tantalum are soluble in CH2Cl2. NMR spectroscopic investigations in solution revealed the formation of isomeric supramolecules owing to the steric hindrance caused by the third tBu group on the Cp′′′ ligand. In addition, a 2D coordination polymer was obtained and structurally characterized.

The reaction of realgar with [Cp′2MH3] in boiling toluene gave [Cp′2M2As2S6] (Cp′ = t-BuC5H4; M = Nb: 1; Ta: 2), while [Cp2WH2] (Cp = C5H5) reacted with As4S4 to give [Cp2W(H)(η1-As5S2)] (6). The structures were determined by X-ray crystallography. Compounds 1 and 2 are dimers in which two Cp′M units are symmetrically bridged by a μ,η2:2-AsS3 ligand, a sulfide ligand and a heteroallylic μ,η2:2-AsS2 ligand. The structure of 6 belongs to the type of bent metallocenes in which tungsten is surrounded tetrahedrally by two Cp ligands, a crystallographically found hydride atom and the new As5S2 cage. The reaction of 1 with W(CO)5THF gave [Cp′2Nb2As2S6·W(CO)5] (3) and [Cp′2Nb2As2S6W(CO)3·W(CO)5] (4). Compound 3 is a monoadduct of 1 bearing the W(CO)5 fragment at the As atom of the AsS3 ligand. The structure of 4 contains a distorted cubane-like Nb2WS4As cluster with an integrated W(CO)3 unit. A similar cluster 5 containing a CuI fragment instead of W(CO)3 was prepared from 1 and CuI. The structure is completed by an attached As4S3 cage, the As3 basis of which is oriented towards iodide. Electrochemical investigations of 1, 3, and 4 shows for each compound quasi-reversible one-electron reductions with E1/2 = −0.73 V (1), −0.55 V (3) and −0.67 V (4), respectively.

The synthesis and characterization of hybrid polymers combining organic P,P′ (dppe) or N,N′ (pyrazine) ligands and inorganic donors (P4S3) as cross-linkers between copper(I) halide aggregates is described. As a simple model system the reaction of a mixture of P4S3, PEt3, and CuX (X = Cl, Br, I) was studied. According to X-ray diffraction analysis, pseudotetrahedral monomers [CuX(PEt3)2(P4S3)] (1–3) were formed, in which P4S3 coordinates through the apical phosphorus atom. Layering a mixture of P4S3, Ph2PCH2CH2PPh2 (dppe), and toluene with CuCl in MeCN under diffusion conditions gives 1D-[CuCl(dppe)(MeCN)] (6), which contains (Cu2Cl2)2(μ-dppe)2 clusters linked by another dppe ligand. The analogous reaction with CuI gives 1D-[CuI(P4S3)(dppe)] (7), which is built up of alternating trans-(Cu2I2)(P4S3)2 units and dppe linkers. Hybrid polymers 2D-[CuX(P4S3)(dppe)] [X = Br (8), I (9)] are formed if CH2Cl2 is used instead of toluene. The 2D structures of 8 and 9 may be derived from that of 7 by connecting neighboring (CuX)(dppe) strands with pairs of inversely coordinated P4S3 cages. Replacement of dppe by pyrazine (pyz) yields 3D-[(CuCl)4(P4S3)2(pyz)] (10) and 3D-[(CuBr)3(P4S3)(pyz)] (12), respectively. The structure of 10 comprises a 3D network composed of alternating, linked 2D-[(CuCl)2(P4S3)] and 2D-[CuCl(pyz)] layers. The structure of 12 contains cradles built from opposing (CuBr)6 rings and pairwise pyz and P4S3 bridges. These cradles are organized into a 3D framework by condensation of the (CuBr)6 rings, and the layers formed are linked by additional pyz molecules. The resulting voids are occupied by toluene molecules. The behavior of P4S3 and P,P′ or N,N′ ligands as competitive building blocks is also expressed by the formation of binary P4S3/CuX or pyz/CuX polymers.

A series of dinuclear halide bridged copper(I) complexes with a central [Cu2(μ-X)2] diamond core (X = Cl, Br and I) and substituted bis(imino)acenaphthene (BIAN) ligands acting as strong π-acceptor subunits was prepared and characterized by elemental analysis, X-ray crystallography and various spectroscopic techniques. In the visible spectral range, the electronic spectra of these deeply colored air-stable compounds are dominated by low-lying charge transfer (CT) transitions. The corresponding broad absorption bands display a bathochromic shift and a decreasing amount of negative solvatochromism in the series X = Cl, Br and I. At the same time, the distance between the two metals becomes shorter and reaches the range of cuprophilic interactions. These systematic trends are interpreted as a decreasing amount of charge transfer character and a more pronounced delocalization between the two copper centers within in the same series.

The diastereomers (RFe,RC)/(SFe,RC)-[CpFe(Prophos)NCMe]X (X = I, PF6), 5:95, differing only in the metal configuration, were prepared from (RFe,RC)/(SFe,RC)-[CpFe(Prophos)I] (95:5) in acetonitrile ...

The coordination behavior of 1,2,4-triphosphaferrocenes [FeCpR(η5-P3C2tBu2)] [CpR = Cp (1), Cp″′ = η5-C5H2tBu3 (3)] towards CuI halides is significantly influenced by the substitution pattern of the cyclopentadienyl ring attached to the iron atom. The reaction of the Cp derivative 1 with CuBr in a 1:1 stoichiometry leads to the dimeric complex [{FeCp(η5:η1:η1-P3C2tBu2)}{μ-CuBr(MeCN)}]2 (5b), in which two 1,2,4-triphosphaferrocenes are linked by two CuBr units. By using a 1:2 stoichiometry, the 1D polymeric compound [{FeCp(η5:η1:η1:η1-P3C2tBu2)}μ-{(CuBr)3(MeCN)2}]n (6) is formed in which the triphosphaferrocenes are bridged by (CuBr)2{CuBr(MeCN)2} units. Starting from CuI, independent of the stoichiometry, the cage compound [{FeCp(η5:η1:η1-P3C2tBu2)}3{Cu(μ-I)}3{Cu(μ3-I)}3{Cu(NCMe)}(μ6-I)](7) is formed. However, if the bulky Cp″′ derivative 3 is used already in a 1:1 stoichiometry with CuBr, a transformation of the initially five-membered 1,2,4-triphospholyl ring into a four-membered 1,2-diphosphete ligand is observed, which is linked by CuBr moieties forming the dimeric paramagnetic complex [{FeCp″′(η4:η1:η1-P2C2tBu2)}(μ-CuBr)]2 (9). Furthermore, applying a 1:2 stoichiometry between 3 and CuX (X = Br, I) the complete fragmentation of the 1,2,4-triphospholyl ring under mild conditions into a tetraphosphabutadiene ligand is observed. In the formed 1D polymeric complexes [{(FeCp″′)2(μ,η4:η1:η1-P4)}{(μ-CuX)2(MeCN)}]n [X = Br (10a), I (10b)] this ligand represents now the middle deck of the triple-decker sandwich complexes linked by four-membered [(CuX)2(CH3CN)] moieties. Moreover, the reaction of the Cp derivative 1 with the Ag salt of the weakly coordinating anion [Al{OC(CF3)3}]4– leads to the dimeric Ag(CH3CN)-bridged dicationic product [{FeCp(η5-P3C2tBu2)}Ag(MeCN)]2[Al{OC(CF3)3}4]2 (11).

1-[2-(Dialkylamino)ethyl]-3-methylimidazolium salts (alkyl = Me (1a), i-Pr (1b)) have been prepared and used as precursors for the synthesis of the corresponding [(NHC)2Ag][AgCl2] complexes (NHC = N-heterocyclic carbene, Me (2a), i-Pr (2b)). Upon treatment of 2a with HBF4, crystals of the unprecedented, NHC-stabilized silver cluster [(NHC)4Ag10Cl10] (5) were obtained and characterized by X-ray diffraction. The crystal structure reveals that the carbene carbon atom exists in the rare μ2-coordination pattern, bridging two Ag(I) atoms with further stabilization of the cluster by numerous argentophilic interactions and a coordination of the amino nitrogen donor to one of the silver atoms. Transmetalation of 2a,b with (R2S)AuCl leads to the respective Au(I) complexes 3a,b, which are further oxidized with Br2 to (NHC)AuBr2Cl (4a,b). In red crystals of 4a the gold atom is coordinated in the unusual square-pyramidal geometry with the amine nitrogen atom in the axial position. Upon dissolution in wet organic solve...

The reaction of the 1,2,4-triphosphaferrocene [Cp*Fe(η5-P3C2tBu2)] (1) with CuX (X = Cl, Br, I) in a 1:1 stoichiometric ratio leads to the formation of the oligomeric compounds [{Cu(μ-X)}6(μ6-X)Cu(MeCN)3{μ,η2-(Cp*Fe(η5-P3C2tBu2))}2{μ3,η3-(Cp*Fe(η5-P3C2tBu2))}] (X = Cl (2), Br (3)) and [{Cu(μ-I)}3{Cu(μ3-I)}3Cu(μ6-I){μ,η2-(Cp*Fe(η5-P3C2tBu2))}3{η1-(Cp*Fe(η5-P3C2tBu2))}] (4) revealing Cu(I) halide cages surrounded by 1,2,4-triphosphaferrocene moieties. The reaction of [Cp*Fe(η5-P3C2tBu2)] with CuI in a 1:4 stoichiometry leads to the formation of the two-dimensional polymer [{Cu(μ-I)}4{Cu(μ3-I)(MeCN)}2{μ3,η3-(Cp*Fe(P3C2tBu2))}]n (5). The oligomeric compounds show dynamic behavior in solution monitored by 31P NMR spectroscopy. All compounds are additionally characterized by single crystal X-ray diffraction.

This work describes the synthesis, crystal structure, and detailed photophysical studies of [n-Bu(4)N][Pt(4,6-dFppy)(CN)(2)] (n-Bu = n-butyl, 4,6-dFppy = (4',6'-difluorophenyl)pyridinate). The material can easily be prepared in high yield and purity by the reaction of [Pt(4,6-dFppy)(H-4,6-dFppy)Cl], [n-Bu(4)N]Cl, and KCN in CH(2)Cl(2). Because of the bulky counterion [n-Bu(4)N](+), Pt-Pt interactions, which frequently lead to aggregate formation, are suppressed in the solid state. Thus, monomer emission is observed. The phosphorescence quantum yield of the neat powder amounts to phi(PL) = 60% at ambient temperature and decays with 19 micros. In tetrahydrofuran (THF) solution, on the other hand, the emission decay time is with 0.26 micros distinctly shorter, and the quantum yield is very low. By means of emission decay time studies in frozen THF and investigations of the highly resolved single crystal emission at 1.2 K, we can assign the emitting T(1) state of the compound as being largely of ligand centered ((3)LC, (3)pi pi*) character. The observed differences of the emission properties of the neat powder compared to the fluid solution are rationalized with an energy stabilization of quenching dd* states in solution because of molecular distortions and/or bond elongations.

A series of pseudo-tetrahedral copper(I) complexes carrying bis(imino)acenaphthene (BIAN) ligands as acceptor subunits and various phosphane derivatives was prepared and characterized by elemental analysis, X-ray crystallography and spectroscopic techniques. The electronic spectra of the compounds are dominated by low-lying metal-to-ligand charge transfer (MLCT) transitions which could be systematically modified by different substituent patterns at the diimine acceptor subunit and by variations of the electron donating properties and bite angles of the phosphane moiety. A qualitative model based on frontier-orbital overlap arguments is introduced to describe the observed variations in optical spectra, excited state energies, solvatochromic behaviour, charge transfer character, and extent of electronic coupling following moderate changes in orbital mixing. Due to their readily tuneable properties and the potential of the BIAN ligands to reversibly store up to four redox equivalents, these systems are of considerable interest for the development of novel multi-electron transfer photosensitizers which are based on the abundant and environmentally benign transition metal copper.

The formation of coordination polymers from copper(I) bromide and P4S3, a potentially tetradentate P-donor bridging ligand, was studied. Whereas (P4S3)3(CuBr)7 (1) formed in excellent yield, (P4S3)(CuBr)3 (2) and (P4S3)(CuBr) (3) crystallized as mixtures. The new compounds were characterized by X-ray crystallography and solid-state 31P MAS NMR spectroscopy. The structure of 1 consists of a 3D network of cylindrical (CuBr)n columns, castellated (CuBr)n chains and diatomic CuBr units. These building blocks are linked by tetradentate P4S3 molecules. The structure of 2 comprises undulated (CuBr)n layers, which are intra- and interlayer linked by tridentate P4S3 molecules. Compound 3 is a one-dimensional polymer composed of four-membered Cu2Br2 rings, which are bridged by the P3 bases of two P4S3 molecules.

The formation of a new type of organometallic-inorganic hybrid coordination polymer from P 4 S 3 ·W(CO) 5 (1) and CuI has been studied. The structure of {P 4 S 3 ·W(CO) 5 }(CuI) (3) has been verified by the combination of spectroscopic (IR, Raman, 31 P MAS NMR) and X-ray diffraction methods. Theoretical studies of β-P 4 S 3 , P 4 S 3 ·W(CO) 5 (1), 1D-(P 4 S 3 )(CuI) (2), and 3D-(P 4 S 3 )(CuI) 3 (4), which may be considered as potential building blocks of 3, were carried out on the DFT level in the crystalline phase. The comparison of calculated and measured vibration modes of the P 4 S 3 cage allows the unequivocal assignment of the recorded Raman shifts between 200 and 480 cm -1 and the determination of the degree of integration of P 4 S 3 within the one-dimensional stacks of 2 or copper iodide networks of 3 and 4.

This paper reports the synthesis, isomer separation, and X-ray characterization of the compounds (SRu,SC)-/(RRu,SC)-[CpRu(Chairphos)Cl], Chairphos = (S)-1,3-bis(diphenylphosphanyl)butane, and cis-/...

Stepwise opening and final removal of the η1-bound Cp* substituents in the bridged pentelidene complexes [Cp*E{W(CO)5}2] (E=P, As) occurs by the reaction with primary phosphines. Not only novel diphospha- and arsaphosphanorbornenes are obtained, but also diastereomerically pure complexed triphosphines. All reaction steps were monitored by NMR spectroscopy, and compounds structurally characterized.

The thermal reaction of trans-1-methyl-2,3-diphenylaziridine (trans-1a) with aromatic and cycloaliphatic thioketones 2 in boiling toluene yielded the corresponding cis-2,4-diphenyl-1,3-thiazolidines cis-4via conrotatory ring opening of trans-1a and a concerted [2+3]-cycloaddition of the intermediate (E,E)-configured azomethine ylide 3a (Scheme 1). The analogous reaction of cis-1a with dimethyl acetylenedicarboxylate (5) gave dimethyl trans-2,5-dihydro-1-methyl-2,5-diphenylpyrrole-3,4-dicarboxylate (trans-6) in accord with orbital-symmetry-controlled reactions (Scheme 2). On the other hand, the reactions of cis-1a and trans-1a with dimethyl dicyanofumarate (7a), as well as that of cis-1a and dimethyl dicyanomaleate (7b), led to mixtures of the same two stereoisomeric dimethyl 3,4-dicyano-1-methyl-2,5-diphenylpyrrolidine-3,4-dicarboxylates 8a and 8b (Scheme 3). This result has to be explained via a stepwise reaction mechanism, in which the intermediate zwitterions 11a and 11b equilibrate (Scheme 6). In contrast, cis-1,2,3-triphenylaziridine (cis-1b) and 7a gave only one stereoisomeric pyrrolidine-3,4-dicarboxylate 10, with the configuration expected on the basis of orbital-symmetry control, i.e., via concerted reaction steps (Scheme 10). The configuration of 8a and 10, as well as that of a derivative of 8b, were established by X-ray crystallography.

Ru(CH═CHFc)Cl(CO)(PiPr3)2 (Fc = ferrocenyl, (η5-C5H4)Fe(η5-C5H5)), 1, has been prepared by hydroruthenation of ethynylferrocene and characterized by NMR, IR, ESI-MS, and Moessbauer spectroscopy and by X-ray crystallography. Complex 1 features conjoined ferrocene and (vinyl)ruthenium redox sites and undergoes two consecutive reversible oxidations. Pure samples of crystalline, monooxidized 1•+ have been prepared by chemical oxidation of 1 with the ferrocenium ion. Structural comparison with 1 reveals an increase of Fe−C and Fe−Cpcentr. bond lengths and ring tilting of the Cp decks, as is typical of ferrocenium ions, but also a discernible lengthening of the Ru−C(CO) and Ru−P bonds and a shortening of the Ru−C(vinyl) bond upon oxidation. This supports the general idea of charge delocalization over both redox sites in 1•+. Band shifts of the charge-sensitive IR labels (ν(CO) for Ru, ν(C−H, Cp) for Fc), the rather small g-anisotropy in the ESR spectrum of 1•+, and the results of quantum chemical calculations i...

Mixed cobalt(III) complexes with diethylenetriamine (Dien) and a tridentate anion of L-ornithine (Orn) [Co(Dien)(His)](ClO4)2 · 0.5 H2O or DL-histidine (His) [Co(Dien)(Orn)](ClO4)2 are synthesized. According to the X-ray diffraction studies, the secondary N atom of diethylenetriamine is trans to the donor N atom of the side chain of the amino acid. Organometallic products of photodecarboxylation of the complexes are isolated by ion exchange chromatography. The electronic absorption spectra indicate that the products contain three-membered Co-C-N rings.

The structures of the crystals of Ba4[trans(N)-Co(Ida)2]3[cis-(N)-Co(Ida)2]2(ClO4)3 · 19.46H2O · 2CH3OH (I) and Ba[trans-(N)-Co(Ida)2]2 · 7H2O (II) (H2Ida is iminodiacetic acid) were determin by X-ray diffraction. The crystals of I containing two geometric isomers of the complex anions [Co(Ida)2]− were obtained by a slow cooling of a hot solution, which contained initially only the cis-isomer. One Ba atom in I interacts with the trans-complex and with two cis-complexes to give a three-dimensional framework in crystal I. The positive charge of the last framework is compensated by one more trans-complex and by the perchlorate ions, one of which acts as a bidentate ligand with respect to the Ba atom. The crystals of II are built of the chains with the alternating Ba atoms and the trans-(N)-[Co(Ida)2]− anions. The other anions of the same structure are each “suspended” to the Ba atoms of the chain.

N1-Aryl(heteroaryl)alkyl-N2-[3-(1H-imidazol-4-yl)propyl]guanidines are potent histamine H2-receptor (H2R) agonists, but their applicability is compromised by the lack of oral bioavailability and CNS penetration. To improve pharmacokinetics, we introduced carbonyl instead of methylene adjacent to the guanidine moiety, decreasing the basicity of the novel H2R agonists by 4-5 orders of magnitude. Some acylguanidines with one phenyl ring were even more potent than their diaryl analogues. As demonstrated by HPLC-MS, the acylguanidines (bioisosteres of the alkylguanidines) were absorbed from the gut of mice and detected in brain. In GTPase assays using recombinant receptors, acylguanidines were more potent at the guinea pig than at the human H2R. At the hH1R and hH3R, the compounds were weak to moderate antagonists or partial agonists. Moreover, potent partial hH4R agonists were identified. Receptor subtype selectivity depends on the imidazolylpropylguanidine moiety (privileged structure), opening an avenue to distinct pharmacological tools including potent H4R agonists.

The coordination behaviour of 1,2,4-triphosphaferrocenes [FeCpR(5-P3C2tBu2)] [CpR = Cp (1), Cp (2)] towards CuI chloride is significantly influenced by the substitution pattern of the cyclopentadienyl ring attached to iron. The dimeric copper complexes [{FeCp(5:1:1-P3tBu2C2)}{-CuCl(MeCN)}]2 (3) and [{FeCp (5:1:1-P3tBu2C2)}(-CuCl)]2 (4), in which two 1,2,4-triphosphaferrocenes are linked by two CuCl centres to form dimeric complexes were obtained in reactions using a 1:1 stoichiometry. Whereas in 3 a tetra-coordinated Cu atom is revealed, 4 possesses a threefold-coordinated Cu atom due to the steric influence of the bulkier Cp ligand. However, if the reaction is carried out with an excess of CuCl in a 1:2 stoichiometry for the Cp derivative 1 the same product 3 is obtained, whereas in the case of a tri-tert-butyl-substituted Cp ligand complex 2 the triphospholyl ring is fragmented under mild conditions to a tetraphosphabutadiene moiety within an iron triple-decker sandwich complex [{(FeCp)2(,4:4:1:1-P4)}{-CuCl(MeCN)}] (5) embedded in a CuCl polymer matrix.

Crystals of Ba[Co(Nta)(C2O4)] · 3H2O were prepared, and their structure was solved by X-ray diffraction (monoclinic space group P21/c), a = 10.0111(10) A, b = 10.2838(6) A, c = 14.2748(15) A, s = 100.350(12)°, Z = 4). The local environment of a Ba2+ ion includes two O atoms of water molecules and seven O atoms of the carboxyl groups of Nta3− and C2O42− ions of five complex anions. Honeycomb type layers can be distinguished in the crystal lattice; within the layers, each Ba2+ atom interacts with three complexes and vice versa. In addition, each Ba atom of the layer is bonded to complexes of the upper and lower layers. Thus, the crystal represents a three-dimensional coordination polymer.

Crystals of Ba3[Co(Nta)2]2 · 10H2O (Nta3− is the ion of nitrilotriacetic acid) are obtained (monoclinic crystal system, a = 17.094(3), b = 13.1873(13), c = 21.490(3) A, β = 98.457(18)°, Z = 4, space group I2/c). The crystal structure of the compound is determined by X-ray diffraction analysis. The crystals consist of the Ba2+ cations, water molecules, and [Co(Nta)2]3− anions in which the donor N and 2O atoms of each Nta3− ion are located at opposite faces of the coordination octahedron. The Co(1, 2) atoms are arranged in the inversion centers. The Ba atoms of the complexes form an intricate three-dimensional framework. One of the two crystallographically nonequivalent complexes binds eight Ba atoms, and another one binds six Ba atoms. The coordination number of the Ba(1) atoms (in the general position) is nine (three O atoms of water molecules and six O atoms of the carboxyl groups of five complexes), and that of the Ba(2) atoms (on the 2 axis) is 6 (two O atoms of water molecules and four O atoms of the carboxyl groups of four complexes).

The novel copper iodide clusters [Cu3(-I)(3-I)2(PH2BH2·NMe3)3] (2) and [Cu4(-I)2(3-I)2(PH2BH2·NMe3)3] (3) were synthesized by treating CuI with the primary phosphine (H2PBH2·NMe3). The novel features of both compounds, which have been characterized by X-ray crystallography, are the unsymmetrical constitution of the copper iodide core due to the influence of the monodentate phosphorus ligand. This results in copper atoms with different coordination numbers within the compound. Complex 2, the major product of the reaction, contains a distorted octahedral Cu3I3-core, in which one vertex is missing. Complex 3 was isolated as a by-product and is composed of a Cu4I4-core in a distorted octahedral coordination.

The reaction of (tht)AuCl (tht = tetrahydrothiophene) with the bulky phosphine ligand Ad2BnP yields [(Ad2BnP)2Au][AuCl2] (1, Ad = 1-adamantyl, Bn = benzyl) as the first example of a 1:1 chloro(phosphine)gold(I) complex having an ionic structure both in solution and solid state. The crystal structure of 1 revealed that the Au(I) atom is linearly coordinated by the phosphorus atoms and effectively shielded from the surroundings by the bulky substituents of the phosphine ligand. For comparison, the analogous complex ( Ad 2 n BuP ) AuCl (2, nBu = n-butyl) has been synthesized and analysed by single crystal X-ray diffraction. In its crystal, it has a common rod-like structure known from R3PAuCl complexes with bulky phosphine ligands.

The products of oxidation of ethylenediaminetetraacetic acid by manganese dioxide have been used to synthesize crystals of [Cu(Edda)(Phen)] · 5H2O (Edda is ethylenediamine-N,N′-diacetate, and Phen is 1,10-phenanthroline). The X-ray diffraction analysis of the crystals shows that the N atoms of the Edda and Phen ligands lie in the equatorial plane around the Cu atom, and the O atoms of the Edda ligands are localized in more remote axial positions. The [Cu(Edda)(Phen)] complexes are grouped in pairs at a distance of 3.46 A between the mean planes of the Phen ligands. Ten water molecules are united by hydrogen bonds into symmetric isolated clusters, and further they form a three-dimensional framework with the [Cu(Edda)(Phen)] complexes.

Oxidation of ( E)-1,2-bis(diphenylphosphanyl)ethene with hydrogen peroxide gave ( E)-1,2-bis(diphenylphosphoryl)ethene. Diels-Alder reaction of ( E)-1,2-bis(diphenylphosphoryl)ethene with cyclopentadiene yielded 2,3-bis(diphenyl--phosphoryl)bicyclo[2.2.1]hept-5-ene (NorphosO). RAC-NorphosO was resolved with O, O-dibenzoyltartaric acid. ( R, R)- and ( S, S)-NorphosO were reduced with trichlorosilane to give 2,3-bis(diphen-ylphosphanyl)bicyclo[2.2.1]hept-5-ene [( R, R)- and ( S, S)-Norphos].

The crystals of Ba2[Cu(Edtp)](ClO4)2 · 5H2O (i) contain the tetragonal-pyramidal complexes of Cu(II) with ethylenediaminetetra-3-propionate ion with one noncoordinated propionate group. The [Cu(Edtp)]2− complex ions and two sorts of the Ba atoms form two-dimensional supramolecular aggregate. Two Ba(1) atoms and one Cu atom form a tetramer by means of the coordinated carboxyl group and a free propionate group. The tetramers are united through the propionate group into ribbons, which are joined by the Ba(2) atoms into the layers. The coordination sphere of each B atom involves four water molecules, including two bridging water molecules. The perchlorate ions are also coordinated by the Ba atoms, one Ba atom acting as a bridge. The structure of the previously studied Ba2[Cu(Edta)](ClO4)2 · 6H2O (II) crystals with the hexadentate ethylenediaminetetraacetate ion is shown to be similar to that of complex I, but in the case of II, the Ba atoms are equivalent as regards the number of the complex anions bound to them.

Reaction of complex [Cp2Mo2(CO)4(micro,eta 2-P2)] (Cp=C5H5 (1)) with CuPF6, AgX (X=BF4, ClO4, PF6, SbF6, Al{OC(CF3)3}4) and [(Ph3P)Au(THF)][PF6] (THF=tetrahydrofuran), respectively, results in the facile formation of the dimers 3 b-h of the general formula [M2({Cp2Mo2 (CO)4(micro,eta 2:eta 2-P2)}2)({Cp2Mo2(CO)4 (micro,eta 2:eta 1:eta 1-P2)}2)][X]2 (M=Cu, Ag, Au; X=BF4, ClO4, PF6, SbF6, Al{OC(CF3)3}4). As revealed by X-ray crystallography, all these dimers comprise dicationic moieties that are well-separated from the weakly coordinating anions in the solid state. If 1 is allowed to react with AgNO2 and LAuCl (L=CO or tetrahydrothiophene), respectively, the dimer [Ag2{Cp2Mo2 (CO)4(micro,eta 2:eta 1:eta 1-P2)}2(eta 2-NO2)2] (5) and the complex [AuCl{Cp2Mo2(CO)4(micro,eta 2:eta 1-P2)}] (6) are formed, which have also been characterised by X-ray crystallography. In compounds 5 and 6, the anions remain coordinated to the Group 11 metal centres. Spectroscopic data suggest that the dimers 3 b-h display dynamic behaviour in solution and this is discussed by using the comprehensive results obtained for 3 g (M=Ag; X=Al{OC(CF3)3}4) as a basis. The interpretation of the experimental results is facilitated by density functional theory (DFT) calculations on 3 g (structures, energetics, NMR shielding tensors). The 31P magic angle spinning (MAS) NMR spectra recorded for the dimers 3 b (M=Cu; X=PF6) and 3c (M=Ag; X=BF4) as well as that of the previously reported one-dimensional (1 D) polymer [Ag2{Cp2Mo2(CO)4(micro,eta 2:eta 1:eta 1-P2)}3(micro,eta 1:eta 1-NO3)]n[NO3]n (4) are also discussed herein and the strong dependence of the chemical shift of the phosphorus atoms within each compound on subtle structural differences in the solid state is demonstrated. Furthermore, the X-ray crystallographic and 31P MAS NMR spectroscopic characterisation of a new polymorph of 1 is reported.

Three 1,1′-disubstituted 4,4′-bi-1H-1,2,3-triazols [R-bta; R = Bn (1), Ph (2), CH2COOH (3)] have been synthesised as bidentate, nitrogen-based ligands by a CuI-catalysed “click” reaction between 1,3-butadiyne and organic azides. Their ligand properties were investigated by preparation of the complexes [RuII(R-bta)3]Cl2 [R = Bn (4), Ph (5), CH2COOH (6)], [(Bn-bta)CuI(DPEPhos)] (7) [DPEPhos = bis{2-(diphenylphosphanyl)phenyl} ether] and [(Bn-bta)ReI(CO)3Cl] (8) following standard reaction procedures. All compounds were analysed by elemental analysis, mass spectrometry and NMR, IR, UV/Vis and luminescence spectroscopy. In addition, the molecular structures of 1–4, 7, and 8 have been determined by X-ray crystallography. In all complexes the Bn-bta acts as a bidentate ligand with structural features comparable to the analogous 2,2′-bipyridine complexes. In their electronic absorption spectra the RuII and ReI complexes exhibit a lowest energy band at around 300 nm, which is substantially higher in energy than in analogous complexes with bpy ligands. All R-bta ligands yield complexes that are not luminescent in solution or in the solid state, which makes these ligands particularly suited for use as spectator ligands. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Crystals of [Cu(Eddp)·(HgCl2)3]n (monoclinic, a = 9.7547(7) A, b = 18.3716(12) A, c = 11.7811(9) A, β = 94.828(9)°, Z = 4, space group P21/n) are made of infinite sheets involving dimeric complexes [Cu2(Eddp)2] interacting with quasi-molecules of HgCl2 (Hg-Cl 2.29-2.36 A). In the dimers, copper atoms are squarely surrounded by two N atoms and two O atoms of the ethylendiamine-N,N′-di(3-propionate) anion, and atom from a neighboring Eddp ion in the apical position; the second apical position is occupied by a Cl atom of one of HgCl2 molecules. Weak Hg-Cl interactions (2.98-3.07 A) join the molecules of HgCl2 in almost planar centrosymmetrical Hg6Cl12 hexamers, and further (Hg-Cl 3.168(3) A, 3.250(2) A) in infinite chains of the hexamers. Finally, the dimeric copper complexes are linked to six Hg atoms of four adjacent hexamers by virtue of their oxygen atoms (Hg-O 2.322(8), 2.609(6) A, 2.730(5) A).

The reaction of [ Cp 2 ∗ Nb ( Te 2 H ) ] (Cp∗ = η5-C5Me5) with [Pd(DBA)2] (DBA = dibenzylidenacetone) and dppm (bis(diphenylphosphanyl)methane) gave the new tetratelluropalladate cluster [ ( Cp 2 ∗ Nb ) 2 PdTe 4 ] (1), which has been characterised by means of elemental analysis, FD-MS and X-ray crystallography. The structure of compound 1 contains a planar PdTe4 rectangle to which two niobocene groups are coordinated. DFT calculations on the hypothetical [PdTe4]2− anion and comparison of the results with those of the W and Ni homologues show that the planar arrangement of Te ligands in 1 is due to the intrinsic property of the central Pd atom.

The crystal structure of Ca[Cr(Edda)(C2O4)]2·5H2O and Ba[Cr(Edda)(C2O4)]2·5H2O (H2Edda — ethylenediamine-N,N′-diacetic acid) was determined by X-ray diffraction analysis. The nearest environment of alkaline earth ions consists of the oxygen atoms of the neighboring [Cr(Edda)(C2O4)]− complex ions (five for Ca and four for Ba) and the water molecules that complete the coordination number to eight. Two atoms and two complex ions are linked into a ring; each Ca atom in the ring is bonded by the oxalate ion bridge to another anion. This results in a centrosymmetric hexanuclear supramolecular assembly. The atoms and the complex anions alternate to form an infinite chain, in which each Ba atom is additionally linked via the oxalate ion bridge with one anion.

The crystal structure of Ba[Co(Cdta)]2 · 9H2O has been determined by X-ray diffraction. The crystals are monoclinic, a = 15.9415(10) A, b = 7.8449(6) A, c = 32.230(2) A, β = 100.387(8)°, Z = 4, space group C2/c)). The cyclohexane-1,2-diaminetetraacetate ion forms the octahedral [Co(Cdta)]− complex through two donor nitrogen atoms and four oxygen atoms and is also connected to two barium atoms through oxygens. The Ba atoms are on a twofold axis. Its nearest environment comprises five O atoms of water molecules, one also being located on a twofold axis, and four O atoms of the four neighboring complex ions. This gives infinite layers parallel to the ab plane. All water molecules form hydrogen bonds within one layer.

The coordination behavior of [(Cp*Mo)2As2S3] (3) (Cp* = C5Me5) toward Cu(I) halides was investigated. One dimensional polymers of the general formula [(Cp*Mo)2As2S3(CuHal)2]n (Hal = Cl, 4; Br, 5) and an oligomer of composition [{(Cp*Mo)2As2S3}3(CuI)7] (6) formed upon the reaction of 3 with the corresponding copper halide. All of the compounds were characterized by ESI−MS, elemental analysis, and single-crystal X-ray crystallography. The solid-state structures of 4 and 5 are isostructural and contain 1D S-shaped chains. This peculiar folding is achieved by alternating planar and folded Cu2Hal2 rings linked together by the central monosulfide bridge of the middle deck of the organometallic unit. The structure of 6 is characterized by a novel [CuI]7 aggregate, which forms a very flat Cu6I3S3 bowl along with three integrated peripheral [(Cp*Mo)2As2S3] building blocks. In contrast to earlier findings, the middle deck of the organometallic units consists in all structures of two trapezoidal AsS dumbbells and one monosulfide ligand.

While reacting the sterically demanding triphosphaferrocene [Cp*Fe(η(5)-P3C2Mes2)] () with Cu(i) halides, the sandwich complex undergoes an unprecedented fragmentation into decamethylferrocene, FeX2 (X = Cl, Br, I) and [P3C2Mes2](-) units. Subsequently, these phospholyl ligands act as versatile, negatively charged building blocks for the formation of supramolecular aggregates representing the monomeric, dimeric and polymeric (1D and 2D) coordination compounds [(P3C2Mes2)2{Cu7(CH3CN)7(μ4-X)(μ3-X)2(μ-X)}{Cu2(μ2-X)2X}{Cu(CH3CN)(μ2-X)}]2·6CH3CN (·6CH3CN: X = Cl, ·6CH3CN: X = Br), [(P3C2Mes2)2{Cu(CH3CN)}6(μ-Br)2(μ3-Br)2{Cu(CH3CN)2Br}2]·CH3CN (·CH3CN), [(P3C2Mes2)4{Cu5(CH3CN)5(μ2-Br)}{Cu(CH3CN)2CuBr2}2{Cu(CH3CN)2}]n(+)[CuBr2]n(-)·2CH3CN (·2CH3CN), [(P3C2Mes2){Cu(CH3CN)(μ-I)}4{Cu(CH3CN)3}]·0.5C7H8·2.5CH3CN (·0.5C7H8·2.5CH3CN), [(P3C2Mes2)Cu7(CH3CN)4(μ4-I)2(μ3-I)2(μ-I)2]x·2C7H8 (·2C7H8), [(P3C2Mes2){Cu(CH3CN)3}2{Cu(μ-I)}6]·0.5CH2Cl2·3CH3CN (·0.5CH2Cl2·3CH3CN) and [Cp*Fe(CH3CN)3]n(+)[(P3C2Mes2)2{Cu(CH3CN)2}{Cu(μ-I)}6]n(-)·0.6CH2Cl2 (·0.6CH2Cl2) with rather non-typical structural motifs within the large varieties of copper halide chemistry. Besides the X-ray structural analyses the obtained assemblies were also characterized in solution in which they undergo fragmentation and re-aggregation processes.

The cobalt atom in the structures studied is situated in the center of an octahedron involving donor atoms N and 3O organic ligands Heida or Bcegly (ions of hydroxyethyliminodiacetate or bis(carbamoylethyl)aminoacetate, respectively), water molecule oxygen atom, and a carboxylic atom of the neighboring ligand in the trans-position to the N atom, so that each (II) ion is linked with two organic anions. This results in a formation of infinite chains — uncharged [Co(Heida)(H2O)]n or cationic {[Co(Bcegly)(H2O)]+}n. In both cases, a molecule of crystallization water is present, and in the second case, the charge of the chains is compensated by perchlorate ions. Aminoacetic cycle of the Heida ligand is approximately coplanar to another such cycle, while a similar cycle of the Bcegly ligand is in the plane of one of six-membered aminopropionamide cycles.

Crystals of Ba Na ethylenediaminetetraacetatocobaltate(III) perchlorate, NaBa2[Co(Edta)]2(ClO4)3 · 9H2O, contain two crystallographically nonequivalent Ba2+ cations and two complex cations [Co(Edta)]− (Edta4− is ethylenediaminetetraacetic acid anion), the latter anions showing opposite chirality. The nearest surrounding of the Ba2+ ions involves three water molecules (including two bridging water molecules), six O atoms of four complexes [Co(Edta)]− and the perchlorate O atom. Tetrameric fragments Ba2(H2O)4[Co(Edta)]2(ClO4)2 are united through the Ba-O bonds into layers with the Ba atoms in the middle of the layers and the perchlorate ions and complex anions at the periphery; in the latter anions, noncoordinated O atom of one of the R-metallocycles is directed outside. The Na atom of the Na(H2O)(ClO4) group located between the layers is bonded to these O atoms of the neighboring layers.

The α-cis-and β-cis-isomers of (triethylenetetramine)(3-sulfinatopropanoato-O,S)cobalt(III) cation were synthesized and crystal structures of their perchlorates were established. The 3-sulfinatopropanoate anion, which forms six-membered ring with the Co atom, is bonded to the latter through the S atom and the carboxyl O atom.

Treatment of the chiral tripod ligand (LMent,SC)-CpH(PNMent) with (Ph3P)3RuCl2 in ethanol afforded the two chiral-at-metal diastereomers (LMent,SC,RRu)- and (LMent,SC,SRu)-[Cp(PNMent)Ru(PPh3)Cl] (70% de) in which the cyclopentadienyl group and the P atom of the ligand coordinated at the metal center. The (LMent,SC,RRu)-diastereomer was isolated by crystallization from ethanol–pentane and its structure was established by X-ray crystallography. The (LMent,SC,RRu)-diastereomer epimerized in CDCl3 solution at 60 °C in a first-order reaction with a half-life of 5.66 h. In alcoholic solution epimerization occurred at room temperature. Substitution of the chloride ligand in (LMent,SC,RRu)- and (LMent,SC,SRu)-[Cp(PNMent)Ru(PPh3)Cl] by nitriles NCR (R = Me, Ph, CH2Ph) in the presence of NH4PF6 gave mixtures of the diastereomers (LMent,SC,RRu)- and (LMent,SC,SRu)-[Cp(PNMent)Ru(PPh3)NCR]PF6. Treatment of (LMent,SC,RRu)- and (LMent,SC,SRu)-[Cp(PNMent)Ru(PPh3)Cl] with piperidine or morpholine in the presence of NH4PF6 led to the chiral-at-metal diastereomers (LMent,SC,RRu)- and (LMent,SC,SRu)-[Cp(PNMent)Ru(PPh3)NH3]PF6 (6% de).

The compound [Co(En)3]2[Hg2(H2O)Cl6]Cl4 (I, En is ethylenediamine) has been synthesized and studied by X-ray diffraction. The crystals of I (a = 21.8745(14) A, b = 10.6008(6) A, c=15.4465(12) A, space group Pna21) consist of tris(ethylenediamine)cobalt(III) complexes (the unit cell contains two [Co(En)3]3+ cations of opposite chirality). [Hg2(H2O)Cl6]2− anions, and isolated chloride ions. The complex anion consists of the tetrahedral [HgCl4]2− group (Hg-Cl, 2.44–2.56 A) and the hydrated molecule [Hg(H2O)Cl2] (Hg-Cl, 2.301 and 2.308 A; Hg-O, 2.788 A) combined by weak Hg-Cl interactions (2.915 and 3.220 A).

Dichloro(ethylenediamone)copper(II) crystals undergo a phase transition at 138 K. X-ray crystal structure analysis at 123 K and 173 K showed that the phase transition is associated with ordering of both carbon atoms; space group changes from P21/m to P21/c, and the c parameter of the unit cell is nearly doubled.

Crystals with uncommon composition NaBa6[Co(Edta)]4(ClO4)9 · 30H2O (Edta4− is ethylenediaminetetraacetic acid anion) were obtained with the following unit cell parameters: a = 14.8513(9) A, b = 26.2361(15) A, c = 15.1789(9) A, α = 91.661(7)°, β = 113.035(7)°, γ = 89.897(7)°, space group P1¯. Each complex anion [Co(Edta)]− is bonded through the carboxyl O atoms to five Ba atoms to give three-dimensional framework in a crystal. One perchlorate ion forms Ba-O-Cl-O-Ba bridge between the Ba atoms; four ClO 4 − ions are isolated, while the remaining four ions act as monodentate ligands at the Ba atoms. The water molecules (25 in sum) complete the coordination sphere of the Ba atoms to eight-, nine-, or ten-vertex polyhedron. Four water molecules are in the closest surrounding of the Na atom, one H2O molecule is isolated.

Methyliminodiacetic acid (H2Mida) and imidazole react with copper(II) to form crystals of the square pyramidal complex [Cu(Mida)Im]. One N and two O atoms of the Mida ligand (Cu-N 2.010(1) A, Cu-O 1.955(1) A, and 1.978(1) A) and the imidazole N atom (1.950(1) A) lie at the base of the pyramid. The carboxyl O atom of the neighboring complex lies at the apical position (2.411(1) A); in this way the individual complexes are linked into infinite zigzag chains. Substitution of imidazole by 1,10-phenanthroline gave [Cu2(Mida)2(Phen)H2O]·2H2O crystals with two nonequivalent centrosymmetric octahedral anions [Cu(Mida)2]2− of face type (Cu-N 2.023 A and 2.028(2) A, Cu-Oax 2.579 A and 2.530(2) A, Cu-Obas 1.952 A and 1.936(2) A). The anions serve as bridges in chains between the [Cu(Phen)H2O]2+ cation fragments to which they are bonded by their axial carboxyl groups. The Cu atom of the cation has a [4+1] environment (with the H2O molecule lying on the axis of the pyramid, and with two N atoms of the ligand and two O atoms of the anions lying at the base).

Crystals of [Ba(H2O)4][Co(Gly)2(NO2)2]2 · 1.43H2O (a=8.1917(6) A, b=8.4440(4) A, c=19.444(1) A, β=98.189(9)°, Z=2, space group P2/n) contain infinite strips of alternating axially symmetric [Ba(H2O)4]2+ fragments and two dinitro-bis(glycinato)cobaltate(III) ions. In addition to four oxygen atoms of water molecules, the nearest environment of Ba includes six oxygen atoms of the carboxyl groups of four anions, two of which are also coordinated by the cobalt atoms (Ba-O, 2.77–3.01 A). The nitrite ions do not interact with the Ba2+ ions.

A series of new carboplatin derivatives was synthesized by introducing fluoro, chloro, bromo and hydroxy substituents into the cyclobutane ring. The carboxylic acid groups were used for the complexation with platinum(II) fragments bearing two ammonia and (RR/SS)-trans-1,2-diaminocyclohexane ligands, respectively, as non-leaving groups. The antiproliferative activity of the new carboplatin analogues differing in the cyclobutanedicarboxylate ligands and the type of platinum fragment were studied in tests with J82 bladder cancer cells and SK-OV-3 as well as cisplatin-resistant NIH:OVCAR-3 ovarian cancer cells. The most active compounds were the 3-fluoro, 3-chloro and 3,3-difluoro derivatives of carboplatin. NMR spectroscopy showed that cis-diammine(3-chloro-1,1-cyclobutanedicarboxylato)platinum(II) was hydrolyzed much faster than carboplatin explaining its higher cytostatic activity.

Reaction of (η6-C6H5CH3)Mo(CO)3 with the easily accessible chiral chelate ligand P,P,Pʹ-tris- [(+)-9-phenyldeltacyclan-8-yl]-1,2-bis(phosphanyl)benzene P-P’ afforded the octahedral molybdenum carbonyl derivate (P-P’)Mo(CO)4 1 as a diastereomer mixture 1a (74%) and 1b (26%). Crystallization gave single crystals of (SP)-(P-P’)Mo(CO)4 1a. The X-ray structure analysis of compound 1a revealed the formation of an unusual triple-decker π-stack in the solid state.

Reaction of [(Cp*MHal)2](μ-Hal)2] (Cp* = η5-C5Me5; M = Rh, Ir; Hal = Cl, Br, I) with the unsymmetrical chelate phosphane P-P‘ (=P,P,P‘-tris[(+)-9-phenyldeltacyclan-8-yl]-1,2-bis(phosphanyl)benzene) in the presence of the metathesis reagents NH4PF6, NaBF4, and NaBPh4 gave [Cp*M(P-P‘)Hal]X (X = PF6, BF4, BPh4; 1−9) in high yields. The P-P‘ ligand, easily accessible from norbornadiene and phenylacetylene in a highly enantioselective synthesis, contains three (+)-9-phenyldeltacyclan-8-yl substituents with a total of 24 homochiral asymmetric carbon atoms. The stereogenic metal center and the secondary phosphorus atom give rise to four diastereomers, all of which are formed in the synthesis of compounds 1−9. Crystallization of the diastereomer mixtures afforded 11 single crystals of compounds 1−9, which served to determine the absolute configurations at the metal atom and the secondary phosphorus atom. Surprisingly, all the compounds with the same configuration adopted almost identical conformations (types I−II...