bluuebunny/crossref_metadata_2025_split huggingface dataset:
Neue Phospholen‐ und Phosphepin‐Derivate aus λ3‐Phosphorverbindungen und Hexafluoraceton oder perfluorierten α‐Diketonen
Authors: Kadyrov Alexander , Neda Ion , Kaukorat Thomas , Sonnenburg Ralf , Fischer Axel , Jones Peter G. , Schmutzler Reinhard 
Published: July 2007

New Phospholene and Phosphepine Derivatives from λ3‐Phosphorus Compounds and Hexafluoroacetone or Perfluorinated α‐DiketonesThe reaction of the bis(2‐chloroethyl)amino‐substituted benzoxazaphosphorinone 1 with hexafluoroacetone (HFA) proceeds with insertion of the carbonyl group of HFA into the heterocycle of 1 to form the oxazaphosphepinedione 2. Triethyl phosphite (3) and triphenyl phosphite (4) react with the perfluorinated diketones 5 and 6 with formation of the pentaoxyphosphoranes 7–10 containing a dioxaphospholene ring system. The reaction of the (2‐chloroethyl)amino‐ and bis(2‐chloroethyl)amino‐substituted 1,3,5,2‐triazaphosphorinanediones 11–14 with the perfluorinated diketone C2F5C(:O)C(:O)CF3 (15) furnishes spirophosphorane derivatives with the dioxaphospholene ring system, 16 and 17, in two cases only. Compound 1 and 2‐[bis(2‐chloroethyl)‐amino]‐4H‐1,3,2‐benzodioxaphosphorin‐4‐one (18) react with the perfluorinated α‐diketones 5 and 6 with insertion of the diketones into the heterocycle of 1 and 18 with formation of compounds 19–22 containing dioxa‐ and oxazaphosphepinone ring systems. The expected oxidative addition of the diketones to λ3P with formation of spirophosphoranes was not observed. Compounds 19–22 were obtained as mixtures of isomers (19a/b–22a/b). Single crystal X‐ray structure analyses were conducted on 2 and 9. The seven‐membered ring of 2 displays a “tub” conformation, with the O and benzo C atoms lying out of the plane of the other four atoms. The two independent molecules of 9 are similar, but differ in the degree of distortion from trigonal‐bipyramidal geometry of phosphorus.
Isolation and Spectroscopic Characterization of Heteroleptic, Anionic and Neutral (Phthalocyaninato)(tetra‐4‐pyridylporphyrinato)lanthanide(III) Double‐Deckers
Authors: Jiang Jianzhuang , Mak Thomas C. W. , Ng Dennis K. P. 
Published: July 2007

AbstractTreatment of 5,10,15,20‐tetra‐4‐pyridylporphyrin [(TPyP)H2] with europium(III) or gadolinium(III) acetylacetonate [Ln(acac)3 · nH2O] (Ln = Eu, Gd) in 1,2,4‐trichlorobenzene produced Ln(acac)(TPyP), which reacted with dilithium phthalocyaninate [Li2(Pc)] to give Li[Ln(Pc)(TPyP)] in moderate yields. Upon exposure to air, solutions of these compounds converted slowly to the corresponding neutral complexes Ln(Pc)(TPyP). The new compounds were spectroscopically characterized.
Komplexe mit Metall‐Phosphor‐Dreifachbindungen als mögliche Intermediate der Umsetzungen von Chlorophosphiniden‐Komplexen mit Metallaten verschiedener Übergangsmetalle
Authors: Scheer Manfred , Schuster Kay , Krug André , Hartung Helmut 
Published: July 2007

Complexes with Metal‐Phosphorus Triple Bonds as Possible Intermediates in the Reactions between Chlorophosphinidenes and Metalates of Various Transition MetalsThe reaction of [{M′(CO)5}2PCl] (M′ = Cr, W) with various metalates ([Cp′Mo(CO)3]−, [Cp * Ni(CO)]−, [Cr2(CO)10]2−) yields the M2P2 tetrahedral complexes [(MLn)2(μ,η2‐ P2){M′(CO)5}2] (MLn = Cp*Ni, M′= Cr (1), W (2); MLn = Cp′Mo(CO)2, M′ = Cr (4); Cp* = η5‐C5Me5, Cp* = η5C5H3tBu2) and the cyclo‐P4 compound [{Cr(CO)4}(η4‐P4){Cr(CO)5}4] 6. As side products the distorted prismane [(Cp*Ni)2{μ4,η4‐(P2‐O‐P2)}{W(CO)5}2] 3 and the diphosphino‐methanone complex [{Cp′Mo(CO)2}2{μ4η2‐PC(O)P}‐{Cr(CO)5}2] 5 are formed. The complexes are characterised by NMR, IR, MS, and X‐ray structure analysis (1‐5). Studying the reaction pathway provided evidence of phosphido intermediates of the type [LnMP→M′Ln].
Metal Complexes with Tetrapyrrole Ligands, LXXII Cerium(IV) Sandwich Complexes with Porphyrin Ligands Linked by Aliphatic and Quinone‐Containing Bridges
Authors: Buchler Johann W. , Heinz Georg 
Published: July 2007

AbstractStarting from 5‐(4‐hydroxyphenyl)‐10,15,20‐tris(4‐methylphenyl)porphyrin (1a), the new bis(porphyrinylphenoxy)alkanes 4a–c were synthesized by ether formation with the α,ω‐dibromoalkanes Br(CH2)nBr (n = 9,10; 3a, b) and 1,4‐bis(3‐bromopropyl)‐2,5‐dimethoxybenzene (3c). The bis‐[(porphyrinylphenoxy)propyl]hydroquinone dimethyl ether 4c derived from 3c was converted into the diporphyrin‐quinone 4e by methyl ether cleavage with BBr3 and subsequent oxidation with ammonium cerium(IV) nitrate. The bisporphyrins 4a–c, e were metalated with cerium(III) acetylacetonate to yield the new cerium porphyrin sandwich complexes 5a–c, e which carry the alkane links in vicinal positions at the porphyrin rings. 5a–c, e were characterized by UV/Vis, IR, 1H‐NMR spectroscopy and cyclic voltammetry. The quinone‐bridged cerium sandwich complex 5e contains the quinone moiety in a distinct non‐coplanar orientation relative to the porphyrin ligands of the double‐decker system. The length of the lateral chains may have a dramatic effect on the first and second oxidation potentials, E3 and E2, of the porphyrin rings: for 5b having 10 aliphatic C atoms in the chain, E3 and E2 are higher by 0.26 and 0.24 V, respectively, as compared with 5a having only 9 aliphatic C atoms. E3 and E2 for the latter are rather close to values for species with dipropylbenzene chains (i.e. in 5c and 5e) or without lateral bridges.
Structural Studies on Indium and Tin Thiobenzoates
Authors: Singh P. , Gupta Vishnu D. , Bhattacharya S. , Nöth Heinrich 
Published: July 2007

AbstractIndium(III) and tin(IV) thiocarboxylates were prepared and characterized on the basis of their IR,13C‐ and19Sn‐NMR data. Indium tris(thiobenzoate) (1) decomposes into a sulfido complex In (S)[S(O)CPh] (2a). The corresponding tris(thioacetate) In[S(O)CMe]3is thermally too unstable to be isolated. The anionic tetrakis complex [Et3NH]{In[S(O)CPh]4} (3) was characterized by X‐ray crystallography which revealed a distorted tetrahedral coordination at the In atom. X‐ray diffraction analysis of the complexes BuSn[S(O)CPh]3(4) and Cl2Sn[S(O)CPh]2(7) showed distorted tetrahedral andcis‐octahedral structures, respectively.
Interaction Modes of Titanium Tetrachloride with the Carbonyl Functionality
Authors: Cozzi Pier Giorgio , Solari Euro , Floriani Carlo , Chiesi‐Villa Angiola , Rizzoli Corrado 
Published: July 2007

AbstractMesityl aldehyde binds TiCl4leading to the first structurally characterized TiCl4‐aldehyde adduct,cis‐[(MesCHO)2TiCl4] (Mes = 2,4,6‐Me3C6H2) (1), which contains a pseudooctahedral titanium and two aldehyde carbonyl groups in acisarrangement. However, in the case of 1:1 TiCl4–acetone adduct [(Me2CO)TiCl3)2(μ‐Cl)2] (3) the solid‐state structure of this acid‐base complex is that of a chloro‐bridged dimer. Both kinds of structures were suggested for the products [{(PhCOMe)TiCl3}2(μ‐Cl)2] (4) and [cis‐(PhCOMe)2TiCl4] (5) formed by the reaction of TiCl4with acetophenone in 1:1 and 1:2 molar ratio. Thioesters behave like acetone in that they give adducts8and9with TiCl4, where9, [{(PhSC(Me)O)TiCl3}2(μ‐Cl)2], exhibits a solid‐state dimeric structure like3. The bidentate bonding mode of the chiral propionyloxazolidone12with TiCl4was revealed by an X‐ray analysis of13.
A Search for Thionitrosyl Chloride (Cl–NS) in the Gas Phase
Authors: Nguyen Minh Tho , Flammang Robert 
Published: July 2007

AbstractAb initio MO calculations at the QCISD(T)/6‐311++G(3df,2p) + ZPE level show that the thionitrosyl chloride ion, ClNS+•, is 36 kJ/mol more stable than the thiazyl chloride ion, NSCl+•, whereas neutral NSCl is 77 kJ/mol more stable than ClNS [IEa (ClNS) = 9.2 ± 0.3 eV, IEa (NSCl) = 10.5 ± 0.3 eV]. Mild flash‐vacuum pyrolysis of the thiazyl chloride trimer (NSCl)3 followed by electron impact ionization resulted in the formation of [N,S,Cl]+• ions (m/z 81). The fragments observed in the CA spectrum of these ions indicate the formation of both NSCl+• and ClNS+• ions. A very weak recovery signal is observed in a neutralizationreionization experiment. This signal is tentatively assigned to the neutral thionitrosyl chloride.
Synthesis and Reactivity of Some Nitroaryl Complexes of HgII and AuIII — Synthesis of a Substituted Biphenyl by C–C Coupling – Crystal Structure of [Hg(C6H4NO2‐3, OnBu‐6)2]
Authors: Vicente Jose , Bermúdez María‐Dolores , Carrión Francisco‐José , Jones Peter G. 
Published: July 2007

Abstract4‐Butoxynitrobenzene reacts with [Hg(O2CCF3)2] and LiCl to give [Hg(R)Cl] [R = C6H3NO2‐3, OnBu‐6 (1)] which is symmetrized by Me4NCl to give [HgR2] (2), the crystal structure of which has been determined. The reaction of 2 with Me4N[AuCl4] affords Me4N[Au(R)Cl3] (3) by a facile transmetallation process. Complex 3 reacts with PPh3 (1:1) to give cis‐[Au(R)(PPh3)Cl2] (4). The diaryl complex [‐Ph‐2)(R)Cl] (5) is obtained by reaction of 3 with [Hg‐(C6H4N=NPh‐2)2] through a second transmetallation reaction. Complex 5 and PPh3 (1:1) give [AuClPPh3] and the C–C coupling biphenyl RC6H4N=NPh‐2 (6).
Compounds of Germanium and Tin, 20. Stannylene Complexes of Iron and Nickel without Donor Stabilization
Authors: Weidenbruch Manfred , Stilter Artur , Peters Karl , Schnering Hans Georg Von 
Published: July 2007

AbstractTreatment of [Fe2(CO)9], [Fe3(CO)12] or [Ni(CO)4] with the alkylarylstannylene RR′Sn: [R= 2,4,6‐tBu3C6H2, R′ = CH2C(CH3)2‐3,5‐tBu2C6H3] furnishes the stannylene complexes [(OC)4Fe=SnRR′] (5) and [(OC)3Ni=SnRR′]. The X‐ray structure analysis of 5 reveals a trigonal‐bipyramidal environment of the iron atom with the tricoordinated tin atom occupying an axial site, thus indicating that RR′Sn: is a strong σ‐donor but weak π‐acceptor.
Characterization of a [4Fe‐4S]‐Ferredoxin Model Based on a Concave Tetradentate Thiol Ligand System
Authors: Martens Constantinus F. , Bongers Mathias M. G. , Kenis Paul J. A. , Feiters Martinus C. , Nolte Roland J. M. , Czajka Ryszard , Linden Johannes G. M. Van Der 
Published: July 2007

AbstractNMR and Mössbauer spectroscopy show that a novel tetrathiol ligand, based on the cavitand diphenylglycoluril, encapsulates a 4Fe‐4S cluster and induces asymmetry in it. The cluster gives a weak electrochemical current response in DMF, with a half‐wave potential for the 2−/3− reduction vs. Fc+/Fc of ‐1.7 V. Ba2+ ions are adsorbed, according to X‐ray analysis of the SEM image of the electrode, and act as modulator and promoter of the electrochemical response. On the basis of cyclic voltammograms it is proposed that this adsorption creates electroactive sites, changing the type of diffusion controlling the mass transport to the electrode from radial to linear, and that it helps the negatively charged complex, which contains a dipole, to approach the negative electrode in an orientation favourable for electron exchange. This feature makes the complex an important model for ferredoxins, in spite of a difference in redox potential.
Hydrogen Bonding and Conformational Analysis of Chelate‐Stabilized Alkoxopalladium(II) Complexes Derived from Amino Alcohol Ligands
Authors: Kapteijn Gerardus M. , Baesjou Patrick J. , Alsters Paul L. , Grove David M. , Koten Gerard Van , Smeets Wilberth J. J. , Kooijman Huub , Spek Anthony L. 
Published: July 2007

AbstractThe reaction of palladium acetate with two equivalents of di‐ and triethanolamines RN(CH2CH2OH)2 in the presence of a base affords the new chelate‐stabilized alkoxo Pd(II) complexes [Pd(OCH2CH2N(R)CH2CH2OH)2] [R = Me (1), Et (2), n‐Bu (3), benzyl (4) or CH2CH2OH (5)]. These N,O‐ligated complexes are isolated in high yield as yellow, crystalline solids and are thermally stable despite the presence of several β‐hydrogen atoms in the ligand system. Both complexes possess a square‐planar palladium coordination geometry with the two oxygen atoms positioned mutually trans. The most notable difference in the molecular structures is that 1 forms a two dimensional network of intermolecular O–HO hydrogen bonds, whereas 5 forms intramolecular O–H ⃛O hydrogen bonds, which cage the palladium center. In solution 1–4 exist as a diastereoisomeric mixture (a racemic enantiomeric pair SNSN, RNRN and a mesomeric form RNSN) in a 1:1 molar ratio, and this ratio is independent of temperature in nonalcoholic solvents, When complexes 1–4 are dissolved in protic solvents (e.g. MeOH) the diastereomeric excess is temperature‐dependent due to an exchange process between the meso diastereoisomer and the (racemic) enantiomeric pair. Thermodynamic parameters for this process in a mixture of MeOH‐toluene have been determined with NMR and show this process to be influenced by the steric nature of the alkyl substituent (R) on nitrogen. A conformational analysis based on 1H‐NMR coupling constants within the N,O‐chelate ring of complexes 1–4 provides details on the solution structure of the ring in both diastereoisomers.
The Synthesis, Crystal Structures and Magnetic Properties of Cu4(AsO4)2(O) and Ba2Cu7(AsO4)6
Authors: Adams Richard D. , Layland Ralph , Payen Christophe 
Published: July 2007

AbstractTwo new compounds Cu4(AsO4)2O (1) and Ba2Cu7As6O24 (2) were obtained from a mixture of CuO and As2O5 · xH2O heated to 1090°C for 72 h in a BaCO3 flux. Compound 1 was obtained as dark green crystals, belonging to the orthorhombic crystal system. Compound 2 was obtained as light gray to colorless crystals belonging to the triclinic crystal system. The structure of 1 contains two copper ions with distorted trigonal bipyramidal geometries and a third with a distorted square pyramidal geometry. One ‚oxide’︁ ion is surrounded by four copper ions in a distorted tetrahedral arrangement. Compounds 2 consists of two chains with alternating units of trigonal bipyramidal CuO5 and square planar CuO4 units, with the oxygen atoms derived from the AsO4 groups. Magnetic susceptibility measurements of 1 and 2 both show effective magnetic moments, μeff1.90–1.95 B.M./Cu at 25°C, which is consistent with Cu2+ ions having one unpaired electron. Significant antiferromagnetic coupling was revealed by variable temperature measurements. At very low temperatures (15–25 K) samples of both 1 and 2 undergo a transition to a weak ferromagnetic state.
Tris(phenylthiomethyl)phosphane Sulfide and Selenide, (PhSCH2)3PX (X = S, Se), as Ambidentate Ligand Systems in Copper(I) Complexes
Authors: Fuchs Stefan , Angermaier Klaus , Bauer Andreas , Schmidbaur Hubert 
Published: July 2007

AbstractTriphenylphosphite has been converted into tris(phenylthiomethyl)phosphane (1) by reaction with LiCH2SPh/DABCO, and subsequently into the corresponding sulfide (2) and selenide (3) by treatment with elemental sulfur or selenium, respectively. Ligands 2 and 3 react with copper(I) halides CuX (X = Cl, Br, I) in polar organic solvents to give either 1:1 (X = Cl: 4, 7, X = Br: 5, 8 ) or 1:2 complexes (X = Br: 9, X = I: 6, 10). The crystal structures of five of these complexes have been determined by single crystal X‐ray diffraction studies. All compounds of the type [(PhSCH2)3PS/Se]CuX (X = Cl, Br) form centrosymmetrical dinuclear complexes featuring a four‐membered ring core Cu2[S/Se], fused to two five‐membered rings Cu[S/Se]PCS through common trans edges. Only one of the three phenyl‐thiomethyl functions is involved in coordination to a metal center. The compound [(PhSCH2)3PS](CuI)2 (6) is associated into a centrosymmetrical tetranuclear complex containing two four‐membered rings (ICu2S) bridged via iodine atoms in 1,3‐cis positions. The ligand is found to employ two of its PhSCH2 functions for metal coordination, giving rise to two five‐membered rings fused to the four‐membered rings via neighbouring edges. In all cases, therefore, the PS/Se functions of the ligands are the preferred donor sites, which are used for the building of bridgehead structural units of polynuclear complexes.
Design of Self‐Adapting N‐Heteroaromatic Substituted Claw Ligands as E−/M+(E = P‐Block Element, M = Main‐Group Metal) Charge Spacers
Authors: Kottke Thomas , Stalke Dietmar 
Published: July 2007

AbstractMonoanionic bi‐ and tridentate ligand systems emulating the structural features of the well‐known poly(pyrazolyl)borates are created by bridging heteroaromatic rings with formally negatively charged p‐block elements. Their properties and versatility are exemplified by their complexes with main group metals. Due to their N(σ)‐donating and π‐interacting ability, as well as the flexibility of the substituent bonding, these ligand systems have the potential to adapt both geometrically and electronically to the coordination requirements of the complexed metal. Within these complexes, the heteroaromatic substituents operate as charge spacers between the formally anionic center and the metal cation without encapsulating either site. This provides possible applications in the creation of reactive soft/hard bimetallic reagents, the realization of multinuclear arrays, and the design of preorganized CVD precursors, particularly en route to III/V‐semiconducting thin films.
Diastereoselectivity in the Reaction of RCH2C[CH2P (Ar)(Lr)]3 with Electrophiles: Enhancement of Diastereoselective Control by η3‐Coordination in {RCH2C[CH2P(Ar)(Li)3}Mo(Co)3
Authors: Büchner Michael , Huttner Gottfried , Winterhalter Ute , Frick Axel 
Published: July 2007

AbstractFollowing a procedure developed for H3CC[CH2P(Ph)2]3 (1a) as the starting compound, various tripod ligands RCH2C[CH2P(Ar)2]3 (1) have been transformed into the trilithiotriphosphides RCH2C[CH2P(Ar)(Li)]3 with various electrophiles R′ — Hal leads to the two diastereomers of RCH2C[CH2P‐(Ar)(R)]3 (6) with an (RRR/SSS : RRS/SSR) ratio close to the statistical value of 1:3, except when ArPh and R′Bzl, where the RRS/SSR diastereomer is obtained almost exclusively. In contrast, the reaction of [RCH2C[CH2P(Ar)(Li)[3]‐Mo(CO)3 (4) with electrophiles R′ — Hal tends to favour the formation of the homochiral RRR/SSS diastereomers. The triphosphide coordination compounds 4 are available by two different routes: either the complexes (RCH2C[CH2P‐(Ar)(H)]3Mo(CO)3, obtained from 2 and (CH3CN)3Mo(CO)3, are deprotonated by MeLi, or the trilithiotriphosphides RCH2C[CH2P(Ar)(Li)]3 are reacted with (CH3CN)3Mo(CO)3 to produce 4 in high yields. The ration in which the two diastereomeric forms of 5 are obtained depends on the nature of the electrophile: the greatest diastereomeric discrimination is obtained for ArPh, RPh, R′Bzl, where the homochiral relative to the RRS/SSR pair. Two‐dimensional NMR spectra and simulations of one‐dimensional spectra are used to ascertain the diastereomeric excess in each case. X‐ray analyses of three compounds of type 5 (5d, ArPh, RH, R′Ph, R′Bzl) indicate the remarkable conformational stability of the tripod metal scaffolding, with the conformations observed for these three compounds in three different solid‐state environments being closely similar, even with respect to the torsional arrangement of the phosphorus‐bound benzyl groups.
Switch from Palladium‐Catalyzed Cycloisomerization/Dimerization of Terminal Allenyl Ketones to Preferential Formation of Monomers by a 5‐Palladatricyclo[4.1.0.02,4]heptane Catalyst: Synthesis of Furans from Substrates Incompatible with the Commonly Used Silver Catalysts
Authors: Hashmi A. Stephen K. , Sehwarz Lothar 
Published: July 2007

AbstractBy making the choice of either PDCl2(MeCN)2 or PTH rac‐4 as catalyst, the allenyl ketones 1 could be preferentially cycloisomerized/dimerized to either 2,4‐disubstituted furans 3 or preferentially cycloisomerized to the monosubstituted furans 2. Since the PTH catalyst tolerates functional groups like terminal alkynes, α‐halogen ketones, and alkyl halides that inhibit the silver catalysis, the latter method is an important extension of Marshall's Ag1‐catalyzed isomerization of 1 to 2. Some of these latter reactions also showed exciting chemoselectivities, e.g. with allenyl ketones, such as 1c and 1d, which also also possess a 1,6‐enyne substructure, no enynecyclization was observed. This is also the first reported example of catalysis by a PTH.
2,4‐Diphosphoranediyl‐1,3‐diphosphetanes
Authors: Schrödel Hans‐Peter , Schmidpeter Alfred 
Published: July 2007

AbstractThe 1,3‐dichloro‐ and 1,3‐dibromo‐substituted title compounds 5b, c result from the condensation of triphenylphosphonium‐bis(trimethylsily1)methylide 1 with PC13 and PBr3. The chloro derivative 5b undergoes a variety of single and double substitution reactions, of which some have merely been tested and others have been made preparative use of. The substitution of one chloride by an ylidyl, amino, phosphino, or metal carbonyl group is accompanied by the spontaneous dissociation of the other P‐CI bond to yield the, 1,3‐diphosphetenium chlorides 14/15, 19, 31 and 36, respectively. In other cases (9, 27, 32) dissociation can be achieved by means of a Lewis acid. Protonation of 5b occurs at the carbon ring members; methylation and formation of transition metal complexes occurs at a phosphorus ring member. PCl3 degrades the four‐membered ring of5b or enlarges the ring to yield 3,5‐diphosphoranediyl‐l,2,4‐triphospholane derivatives 39, 40, 42.
Palladacycles as Reactive Intermediates
Authors: Dyker Gerald 
Published: July 2007

AbstractPalladacycles are discussed as the key intermediates of some important preparative ring forming reactions; their reactivity depends strongly on the ring size. The existence of 5‐membered palladacycles, and even 4‐membered palladacycles, is now firmly established, whereas the knowledge of 6‐membered and larger palladacycles is based mainly on mechanistic considerations. The role of 5‐membered palladacycles as catalysts is described briefly.
Reactions of Complex Ligands, LXXVII. Axial‐Chiral Metal Carbenes: Synthesis and Structure of 1,1‐Binaphthyl‐Derived Carbonyl‐Carbene Complexes of Chromium
Authors: Heinz Dötz Karl , Tomuschat Philipp , Nieger Martin 
Published: July 2007

AbstractAxial‐chiral mono‐ and biscarbene complexes of chromium containing the 1,1‐binaphthyl skeleton have been obtained in both racemic and enantiopure forms in a one‐pot reaction starting from lithiated 2,2‐dimethoxy‐1,1‐binaphthyl (1) and hexacarbonyl chromium via the Fischer route. An X‐ray structure analysis of the biscarbene complex 2 reveals that the biscarbene functionalization significantly increases the dihedral angle defined by the biaryl planes. The enantiopure complexes have been characterized by CD spectroscopy.
Formation of the Cationic [(2‐Aminoethenyl)carbine]iron Complexes by Treatment of (2‐Methoxyethenyl)carbene Complexes with Primary Amines:Synthesis and Characterisation
Authors: Kühn Jürg , Schollmeyer Dieter , Rü‐Braun Karola 
Published: July 2007

AbstractCationic (2‐methoxyethenyl)methoxycarbene iron complexes 2, [Cp(CO)2Fe(C(OMe)CHCR(OMe))+][PF6−], are obtained by the addition of methanol to the corresponding (alkynyl)‐methoxycarbene complexes 1, [Cp(CO)2Fe(C(OMe)CCR)+][PF6−]. Primary amines, H2NR', react with these 1,3‐dimethoxy‐substituted (alkenyl)carbene complexes, 2, through an addition/elimination process to yield cationic (2‐aminoethenyl)methoxycarbene iron complexes, 3, [Cp(CO)2Fe(C(OMe)CHCR(NHR'))+][PF6−] in an isolated yield of 71–90%. The complexes 3a–c were characterized by X‐ray structural analyses. Thus, previously isolated products, from the reaction, of the (alkynyl)methoxycarbene complexes 1a and 1c, with aniline at room temperature, are assigned to the structures 3c and 3e. The spectroscopic and structural data obtained are discussed.
Metal Complexes of Biologically Important Ligands, XCIV. Hexanuclear Isocyanide and Carbene Metal Complexes from Neomycin B
Authors: Krawielitzki Stefan , Beck Wolfgang 
Published: July 2007

AbstractFrom the amino glycoside neomycin B, the acetate‐protected hexaisocyanide 4 has been prepared. 4 forms the hexanuclear complexes [(4)(AuCl)6] (5), {(4)[Cr(CO)5]6}, {(4)[MCl2(η5‐C5Me5)]6} (M = Rh, Ir), {(4)[RuCl2(p‐cymene)]6}, {(4)‐[MCl2(PR3)]6} (MPd, Pt), and 4{(4)[PdCl(C6H4CH2NMe2)]6). The hexaisocyanohexagold(I) complex 5 reacts with H2NtBu and PhNH2 to give the corresponding carbene complexes. The compounds have been characterized by IR, 13C‐ and 31P‐NMR spectroscopy, and (partially) by FAB‐MS data.