bluuebunny/crossref_metadata_2025_split huggingface dataset:
Mono‐ und Diferriophosphane und ‐thioxophosphorane
Authors: Lorenz Ingo‐Peter , Mürschel Petra , Pohl Wolfgang , Polborn Kurt 
Published: July 2007

Mono‐ and Diferriophosphanes and ‐thioxophosphoranesHerrn Professor Dr. Ekkehard Lindner zum 60. Geburtstag gewidmet.
The substitution of organic substituents in phosphanes or thioxophosphoranes by the 17‐electron fragments CpFe‐(CO)2 (Fp) leads to isolobal ferriophosphanes or ‐thioxophosphoranes. The mono‐ and diferriophosphanes FpnPPh3−n [n = 1 (3), 2 (4)] are obtained by deprotonation of the mono‐ and diferriophosphonium salts [FpnPPh3−nH]X [n = 1 (1), 2 (2)] with DBU. They are oxidized by sulfur giving the mono‐ and diferriothioxophosphoranes FpnPPh3−n(S) [n = 1 (5), 2 (6)]. Sulfide 5 arises also from the reaction of CpFe(CO)2Cl and Ph2PH(S)/DBU. The one‐sided decarbonylation reaction of 6 leads to FpFp′PPh(S) (7, Fp′ = CpFeCO). The Fp substituents (17 electrons) in 3–7 coordinate as one‐electron donors to the PhnP‐ or PhnP(S) units (n = 1, 2). The bridging functions in 4 and 6 are hitherto unknown. The molecular structures of the complexes 5–7 were determined by X‐ray structure analyses.
Chiral Ligands for Transition Metal Complexation
Authors: Crisci Gerardo , Hahm Torsten , Weaver George W. , Winterfeldt Ekkehard 
Published: July 2007

AbstractNovel chiral salen‐ or salphen‐type ligands with stereogenic centres in the 1,3‐dicarbonyl moiety 2 as well as in the amino bridge in 15–18 were synthesized from the enantiomerically pure Hajos‐Wiechert ketone.
Structure and Conformation of Bis(trifluoromethylthio)methane, CH2(SCF3)2
Authors: Korn Monika , Haas Alois , Oberhammer Heinz 
Published: July 2007

AbstractThe geometric structure and conformational properties of bis(trifluoromethylthio)methane, CH2(SCF3)2' were determined by gas electron diffraction. The main conformer (70 ± 15%) possesses C2 symmetry with dihedral angles Φ(SCSC) = 79.1(10)°. The second conformer possesses C1 symmetry. The following skeletal geometric parameters (distances ra [pm] and angles 〈α[°] with 3‐σ uncertainties) were obtained: CS 183.6(3), SCF3, 179.3(3), SCS 112.1(6), and CSC 98.2(10). The geometric structures and relative conformational stabilities were well reproduced by ab initio calculations at the HF/3‐21G* level.
Reactions of Phosphaalkenes with Hexafluoroacetone
Authors: Müller Christian , Bartsch Rainer , Fischer Axel , Jones Peter G. , Schmutzler Reinhard 
Published: July 2007

AbstractThe dimethylamino‐substituted phosphaalkene 1 reacts with hexafluoroacetone (HFA) with addition at the PC bond to form the 1,5,2‐dioxaphosphorinane 2. The structure of 2 was confirmed by an X‐ray crystal structure analysis. The six‐membered ring displays an envelope conformation with the phosphorus atom out of the plane, but the phosphorus is disordered over two sites. Reaction of P‐trimethylsilyl‐substituted phosphaalkenes with HFA proceeds with retention of the PC double bond and insertion of HFA into the PSi bond. Two isomeric products are obtained and are characterized by 1H‐, 13C‐, 19F‐, and 31P‐NMR spectroscopy, IR spectroscopy, mass spectrometry, and elemental analysis.
Photochemische Reaktionen von Übergangsmetall‐Organyl‐Komplexen mit Olefinen, 13Photochemisch induzierte [5+2],homo[5+21‐Cycloaddition von 3‐Hexin an Tricarbonyl(η5‐2,4‐cycloheptadien‐l‐yl)mangan
Authors: Kreiter Cornelius G. , Fiedler Christian , Frank Walter , Reiß Guido J. 
Published: July 2007

Photochemical Reactions of Transition Metal Organyl Complexes with Olefins, 1312. Mitteilung: Lit.

. – Photochemically Induced [5+2],
homo
[5+2] Cycloaddition of 3‐Hexyne to Tricarbonyl(η
5
‐2,4‐cycloheptadien‐1‐yl)manganeseTricarbonyl(η5‐2,4‐cycloheptadien‐1‐yl)manganese (1) reacts upon UV irradiation in hexane at 243 K with two equivalents of 3‐hexyne (2) in successive [5+2],homo[5+2] cycloadditions to give tricarbonyl(η2:2:1‐1,2,3,11‐tetraethyltricyclo‐[5.3.1.04,10]undeca‐2,5‐dien‐11‐yl)manganese (3). Its crystal and molecular structure was determined by an X‐ray diffraction analysis, in solution it was studied also by IR and NMR spectroscopy.
Pentamethylcyclopentadienyl Iridium Complexes Containing Chalcogenido Ligands: Reactions of Cp*Ir(CO)2 with Elemental Sulfur and Selenium
Authors: Herberhold Max , Jin Guo‐Xin , Milius Wolfgang 
Published: July 2007

AbstractPhotolysis or thermolysis of Cp*Ir(CO)2 (1) in the presence of excess sulfur (S8) gives Cp*Ir(CO)(S4) (2a) which is further decarbonylated to [Cp*Ir(μ‐S4)]2 (4a). The analogous reaction of 1 with excess selenium leads to Cp*2Ir2(μ‐Se)(μ‐Se4) (6b). In the case of limited chalcogen supply, the products are [Cp*Ir(CO)(μ‐E)]2 [E = S (3a), Se 3b)] and [Cp*Ir(μ‐E)]4 [E = S (5a), Se (5b)]. A stepwise formation of the pseudocubane clusters 5a,b from dinuclear precursors is assumed. The solid‐state structure of 2a has been determined by X‐ray crystallography.
Reactions at Silicon‐Silicon Bonds, V. Selective Trichlorosilylation of Alkyl(diorganylamino)chlorophosphanes with Hexachlorodisilane or with Trichlorosilane/Triethylamine. ‐ Two Routes to New Functional Trichlorosilylphosphanes
Authors: Müller Lutz‐Peter , Mont Wolf‐Walther Du , Jeske Jörg , Jones Peter G. 
Published: July 2007

AbstractThe reaction of alkyl(diorganylamino)chlorophosphanes R(R2′N)PCl 1 (1a: R = tBu, R′ = Et, 1b: R = iPr, R′ = iPr; 1c: R = iPr, R′ = Ph) with hexachlorodisilane, afforded alkyl(diorganylamino)trichlorosilylphosphanes R(R2′N)PSiCl3 2 (2a: R = tBu, R′ = Et; 2b: R = iPr, R′ = iPr; 2c: R = iPr, R′ = Ph) and silicon tetrachloride. An intermediate formed in the reaction of 1b with hexachlorodisilane, the adduct iPr(iPr2N)(Cl)P‐Si(Cl)3‐SiCl3 (3b = 1b · Si2Cl6), was detected by 31P‐ and 29Si‐NMR spectra that indicate pentacoordinated silicon bound to tetracoordinated phosphorus and tetracoordinated silicon. Trichlorosilylphosphanes 2 are also available from 1 under very mild conditions by reductive trichlorosilylation with trichlorosilane in the presence of triethylamine. Compounds 2 were identified analytically, by mass spectroscopy, multinuclear NMR, and an X‐ray structure determination of 2c.
Darstellung von phosphorhaltigen Heterocyclen aus 2‐Aminonicotinsäure
Authors: Sonnenburg Ralf , Neda Ion , Fischer Axel , Jones Peter G. , Schmutzler Reinhard 
Published: July 2007

Synthesis of Phosphorus‐Containing Heterocycles from 2‐Aminonicotinic AcidThe reaction of 2‐aminonicotinic acid with ethyl chloroformate, followed by alkylation with NaH/Mel and decarboxylation with methylamine, led to N‐methyl‐2‐(methylamino)nicotinamide (3). Treatment of 3 with PCl3 in the presence of triethylamine gave the phosphorinanone 4. Substitution of chlorine in 4 by the dimethylamino‐, N,N,N′‐trimethylethylenediamino‐, or bis(2‐chloroethyl)amino group furnished 5–7. Hydrolysis of 4 with small amounts of water formed the phosphoryl derivative 8 as the hydrochloride. The spirophosphoranes 9 and 10 were produced by reaction of 5 with hexafluoroacetone and tetrachloro‐o‐benzoquinone, respectively. In order to evaluate its coordination ability, the N,N,N′‐trimethylethylenediamino‐substituted diazaphosphorinanone 6 was allowed to react with the tetracarbonyl norbornadiene derivatives of chromium(0) and molybdenum(0). The cis‐substituted tetracarbonyl complexes 12 and 13 were formed. In the reaction of 7 with dichloro(1,5‐cyclooctadiene)platinum(II) the cis‐disubstituted complex 15 was formed. A comparison of benzo‐ and pyrido‐annulated phosphorinanones was made, and their differences were discussed. In the case of the compounds 2, 7, and 9 singlecrystal X‐ray structure analyes were performed. In 9 the heterocycle C and N atoms are coplanar (the phosphorus lies 60 pm outside the plane); P and N(2) are displaced in 7 to the same side of the plane of the remaining four atoms.
Ligandgesteuerte P2‐Verknüpfung zu einem acyclischen P4‐Liganden
Authors: Scherer Otto J. , Berg Gerald , Wolmershäuser Gotthelf 
Published: July 2007

Ligand‐Induced P2 Coupling to an Acyclic P4 LigandThe further terminal coordination of M(CO)5 (M = Cr, Mo W) to [(Cp‴Co)2(μ‐η2:2‐P2)2] (1), Cp‴ = 1,2,4‐tBu3C5H2, affords the polynuclear cobalt complexes [(Cp‴Co)2(μ3(4)‐η4:4:1:(1)‐P4){M(CO)5}n], n = 1; M = Cr (2a), Mo (2b), W (2c) and n = 2, M = W (3). The X‐ray crystal structure analyses as well as low‐temperature 31P‐NMR studies show that in 1 the two P2 ligands are rectangularly oriented while in 2b, 2c, and 3 they are coupled to an acyclic, trapezoidally arranged P4 chain.
A Deceiving X‐ray Single‐Crystal Structure Determination: Amino‐Hydrogen Exchange in Amino‐alkynylboranes and ab initio Investigations of Alkynylboranes, Borirenes, and Boraallenes
Authors: Metzler Nils , Nöth Heinrich 
Published: July 2007

AbstractDimeric(dimethylamino)(phenylethynyl)borane (2)2 is formed by the reaction of bis(dimethylamino)(phenylethynyl)‐borane (1) with 9‐BBN‐H. An X‐ray single‐crystal diffraction study revealed a central B2N2 four‐membered ring for (2)2 with both alkynyl groups pointing to the same side in a cisoid arrangement. However, solution and solid‐state NMR as well as ab initio calculations on model compounds show that the cis arrangement in the crystal chosen for X‐ray diffraction is not representative of the bulk material, which consists of both cis and trans isomers. Further investigations of the competition between hydrogen‐amino group exchange and hydroboration in the reaction of amino‐alkynylboranes with hydroborating agents (9‐BBN‐H and catB‐H) show the exchange to be much faster even in the presence of Wilkinson's catalyst and with cyclic amino‐alkynylboranes such as 1,3‐dimethyl‐2‐[(trimethylsily1)ethynyl]‐1,3,2‐diazaborolidine (3). Ab initio calculations on alkynylboranes I, borirenes II, and boraallenes III, which are all geometrical isomers, show alkynylboranes to be the most stable isomers only if strongly π‐donating groups X (X = NH2, F) are attached to the boron atom. In any case, boraallenes are highest in energy.
Silylimido and Disilylamido Groups as Clustering Centers for (Phosphane)gold(I) Units: Aurated Silylammonium Cations
Authors: Angermaier Klaus , Schmidbaur Hubert 
Published: July 2007

AbstractThe reaction of hexamethyldisilazane with tris[(phosphane)‐aurio(I)]oxonium tetrafluoroborates affords the corresponding trinuclear μ3‐trimethylsilylimido compounds of the type {[(R3P)Au]3NSiMe3}+ BF−4 (1a‐f). With (triphenylsilyl)amine and the oxonium reagents the analogous series of Ph3Si derivatives (2a‐f) is formed (R = Me, Et, iPr; R3 = Ph2Me; R = Ph, o‐Tol). The Et3P‐based oxonium salt and (Me3Si)2NH give the dinuclear μ‐trimethylsilylamido complex {[(Et3P)Au]2N(SiMe3)2)2}+ BF−4 (3) as the main product. The crystal and molecular structures of complexes 2a, 2e, and 3 were determined. The trinuclear cations have a pseudo‐tetrahedral structure with small Au‐N‐Au angles and short Au‐Au distances for the SiNAu3 units. The Ph3SiN units in 2a and 2e are capping triangles of gold atoms, while in the cation of 3 the (Me3Si)2N unit is bridging a pair of gold atoms. In the 31P‐ and 14N‐NMR spectra of compounds 1 and 2 (except for 1f and 21) the coupling J(31P,14N) is observed. This coupling is temperature‐dependent, owing to changes in the relaxation characteristics in solution at low temperature. The decomposition of compounds 1 and 2 leads to the formation of pentanudear dications {[(R3P)Au]5N}2+ for R = Me, Ph.
Chiral Organometallic Reagents, XVI. Enantiomerization of α‐Thio‐, α‐Seleno‐, and α‐Telluro‐Substituted Alkyllithium Compounds; Kinetic and Mechanistic Studies
Authors: Hoffmann Reinhard W. , Dress Ruprecht K. , Ruhland Thomas , Wenzel Andreas 
Published: July 2007

AbstractThe rate of enantiomerization of the racemic α‐phenylselenoalkyllithium compound 6 has been determined by dynamic NMR spectroscopy in [D8]THF. The enantiomerization rate was found to be first order with respect to monomeric 6 and to show no conspicuous solvent dependence (diethyl ether; toluene + 1 eq. of THF) or change upon addition of LiClO4. The marked steric effects on the enantiomerization rate found with the α‐duryl‐ and α‐mesityl‐selenoalkyllithium compounds 7c and 7d suggest that rotation about the carbanion‐selenium bond may be the rate‐determining step in those sterically hindered systems. Similar steric effects were detected for the enantiomerization of the corresponding α‐arylthio‐ and α‐aryltelluroalkyllithium compounds 7j and 7f, but are absent with the α‐arylsilyl‐substituted alkyllithium compound 7o. This finding, along with the fact that the phenyltelluro‐ (7e), phenylseleno‐ (6), and phenylthio‐alkyllithium compounds (7g) have essentially the same enantiomerization barrier, lead us to propose that in these cases a reorganization within the contact ion pair is the rate limiting step for the enantiomerization.
Bis(cyclopentadienyl)methane‐Bridged Dinuclear Complexes, 10 The Bis(cyclopentadienyl)methane Link between Lewis Basic and Lewis Acidic Metal Centers
Authors: Stempfle Bernd , Schmidt Simone , Sundermeyer Jörg , Werner Helmut 
Published: July 2007

AbstractThe mononuclear rhodium complexes [(C5H5CH2C5H4)‐Rh(CO)2] (1) and [(C5H5CH2C5H4)Rh(PhCCPh)(PiPr3)] (2) readily react with nBuLi or TlOEt to yield the corresponding lithium salts 3 and 4 or thallium salts 5 and 6. The reaction of these salts with [(C5H5)Nb(NtBu)Cl2] (7) leads to the formation of the heterodinuclear compounds [{CH2(C5H4)2}‐{Rh(CO)2}{(C5H5)Nb(NtBu)Cl}] (8) and [{CH2(C5H4)2}‐{Rh(PhCCPh)(PiPr3)}{(C5H5)Nb(NtBu)Cl}] (9), respectively. Treatment of 3–6 with [Mo(NtBu)2Cl2] (10) gives the heterodinuclear Rh/Mo complexes [{CH2(C5H4)2}{Rh(CO)2}‐{Mo(NtBu)2Cl}] (11) and [{CH2(C5H4)2}{Rh(PhCCPh)‐(PiPr3)}{Mo(NtBu)2Cl}] (12). The analogous reaction of [Mo(NMes)2Cl2(DME)] (13) with 3–6 yields the corresponding complexes [{CH2(C5H4)2}{Rh(CO)2}{Mo(NMes)2Cl}] (14) and [{CH2(C5H4)2}{Rh(PhCCPh)(PiPr3)}{Mo(NMes)2Cl}] (15). From the monometallated ligand [(C5H5CH2C5H4)M] (M = Li: 16; M = Tl: 17) and the imidometal compounds 7, 10 and 13, the mononuclear complexes [(C5H5CH2C5H4)(C5H5)Nb‐(NtBu)Cl] (18) and [(C5H5CH2C5H4)Mo(NR)2Cl] (R = tBu: 19; R = Mes: 20) have been obtained.
Synthesis and Properties of (Tetra‐tert‐butylphthalocyaninato)ruthenium(II) and (Tetra‐tert‐butyl‐2,3‐naphthalocyaninato)ruthenium(II)
Authors: Hanack Michael , Knecht Siegfried , Polley Rainer 
Published: July 2007

AbstractThe first synthesis of pure tert‐butyl‐substituted (phthalocyaninato)‐ and (2,3‐naphthalocyaninato)ruthenium [(tBu)4‐MacRu] by thermal decomposition of (tBu)4MacRu(L)2 (L = 3‐chloropyridine, ammonia) is described. The compounds were characterized by UV/Vis, IR, and NMR measurements.
The First Titanacyclic Five‐Membered Cumulene. Synthesis, Structure, and Reactivity
Authors: Burlakov Vladimir V. , Ohff Andreas , Lefeber Claudia , Tillack Annegret , Baumann Wolfgang , Kempe Rhett , Rosenthal Uwe 
Published: July 2007

AbstractThe first five‐membered titanacyclic cumulene (5) was prepared by treatment of the titanocene generator Cp2Ti(Me3SiC2SiMe3) with the di‐tert‐butylbutadiyne in a molecular one‐to‐one ratio. The reaction of 5 with “Cp2Zr” or of the analogous complex with “Cp2Ti” leads to cleavage of the central C‐C bond in the metallacyclocumulene complexes to afford the same product, the heterodimetallic ρ, π,‐alkynyl‐bridged titanocene‐zirconocene complex Cp2Zr(μ‐η1η2‐C≡CtBu)Cp2Ti(μ‐η1η2‐C≡CtBu) (6), in which each alkynyl group is π‐bonded to one and π‐bonded to the other metal as shown by X‐ray diffraction studies. In solution the two alkynyl groups become equivalent. The coupling reaction of “Cp2Ti” with bis(trimethylsilyl)butadiyne in a one‐to‐two molecular ratio leads to the unsymmetrically substituted titanacyclopentadiene (7).
Preparation, Properties, and Reactions of Metal‐Containing Heterocycles, XCI. Insertion of Activated Alkynes and Sulfur into the P‐P Bond of Diphosphamolybdacyclopropanes
Authors: Lindner Ekkehard , Kneißle Wilfried , Fawzi Riad , Steimann Manfred , Mayer Hermann A. , Gierling Karlheinz 
Published: July 2007

AbstractThe insertion of the alkynes ZC≡CZ (2a‐i) [Z = Co2R: R = Me (a), Et (b), nPr (c), iPr (d), nBu (e), tBu (f), neo‐Pent (g), cyc‐Hex (h); Z = CF3 (i)] into the P1‐P2 bond of the diphos‐phamolybdacyclopropane Mes (1) (Mes = 2,4,6‐trimethylphenyl) results in the formation of the diphosphamolybdacyclopentenes Mes (3a‐i). According to an X‐ray structural analysis, 3a crystallizes in the space group P21/c with the mesityl function at P2 and the cyclopentadienyl fragment at the metal atom on the opposite side of the planar five‐membered ring. The same orientation is found in solution by NMR experiments (NOE; 2D 1H, 13C HETCOR). Kinetic investigations confirm that the rate constants decrease in the sequence R = Me > Et > nPr > isoProp > Cy > nBu > neo‐Pent > tBu. The second‐order reaction and the strongly negative activation entropy which was determined in the case of the reaction 1 + 2e → 3e are consistent with a nucleophilic attack of P2 at one of the triply bonded carbon atoms of the alkyne. The reaction of 3a, h with sulfur affords the diastereomeric compounds Mes (4a, h). An X‐ray structural analysis of the heterocycle 4h, which crystallizes in the space group P1, shows the presence of the enantiomeric pair SR/RS. The reaction of 1 with alkynes is hindered if this heterocycle is oxidized by sulfur to give Mes (5). Further reaction of 5 with sulfur leads to the ring‐expanded heterocyclic intermediate (6) which crystallizes in the space group P1. The five‐membered ring in 6 has an envelope conformation. Upon thermally induced cleavage of the P2S2Mes fragment from 6 the three‐membered ring (7) is formed as the final product.
Reactions of Complex Ligands, LXVI. Diastereomerically Pure 2‐Ethynylcyclopropanecarboxylic Acid Derivatives and (2‐Ethynylcyclopropyl)methoxycarbene Complexes of Chromium and Tungsten
Authors: Kretschik Oliver , Nieger Martin , Dötz Karl Heinz 
Published: July 2007

AbstractEthynylcyclopropanecarboxylic acid esters 2c/2t were prepared from phenylbutenyne 1 and ethyl diazoacetate. Pure diastereomers were obtained by chromatography and converted into the corresponding acyl chlorides 4c/4t. Reaction with K2[M(CO)5] (M = Cr, W) affords alkynylcyclopropylcarbene complexes of chromium 7c/7t and tungsten 8c/8t. An X‐ray structure analysis of 7t reveals a distorted cyclopropane skeleton.
Polare Iminoborane: Reaktionen des (tert‐Butylimino)(pentafluorphenyl)borans
Authors: Klöfkorn Christiane , Schmidt Martin , Spaniol Thomas , Wagner Trixie , Costisor Otilia , Paetzold Peter 
Published: July 2007

AbstractPolar Iminoboranes: Reactions of (tert‐Butylimino)(pentafluorophenyl)boraneThe reactions of the iminoborane C6F5‐B≡N‐tBu (1) with nitriles and isonitriles are studied. Nitriles RCN give cycloadducts either of the triazadiboracyclohexane type (3a; R = iPr) or of the tetrazatriborabicyclo[4.2.0]octane type [4b‐d; R = Ph, p‐C6H4Me, p‐C6H4(CF3)] or of the (iminomethyl)borazine type (5e, f; R = Me, Et). Isonitriles RNC yield mainly adducts of RNC to a cycloaddition product of the diazadiboracyclopentane type (6a, b; R = 2,6‐C6H3Me2, tBu); the adduct of RNC to a diazadiboracyclobutane may be a side‐product (7b; R = tBu). The iminoborane Me3Si(tBu)N‐B=NtBu reacts with two molecules of (2,6‐C6H3Me2)NC to give the corresponding azaboracyclobutane 8. The iminoborane tBu‐B≡N‐C6F5 (1′), formed by gas‐phase elimination of ClSiMe3 from Cl(tBu)B = N(C6F5)SiMe3 (9), cyclodimerizes more readily than the isomeric borane 1. The cyclodimer 2′ gives 1:1‐addition reactions with tBuNC, PMe3, and MeNC, respectively; the added components fluctuate in solutions of the products 7b'‐d'. A similar fluctuation is observed with the 1:1 adduct 7c from PMe3 and the cyclodimer 2 of the iminoborane 1. The products 3a, 5e, 6a, 8 crystallize in the space groups P21/c, P21/n, Pbca, and P21/c, respectively.
The Reaction of RLi Species with CO and Isonitriles: IR Spectroscopic Investigations in Liquid Xenon and Ab‐Initio Calculations of the Intermediates
Authors: Tacke Matthias 
Published: July 2007

AbstractSolutions of alkyl‐ or aryllithium compounds were treated with CO or tBu‐NC in liquid xenon (LXe) at low temperature. Carbonyllithium compounds, acyllithium and the corresponding isolobal isonitrile products were characterized by IR spectroscopy for the first time. The structures, energies and characteristic IR frequencies of the intermediates were calculated by using ab‐initio methods and discussed with the experimental values.
Addition von Hydrofullerid [C60H]− an koordinierte, ungesättigte Kohlenwasserstoffe: Bindung von Fulleren an Metallkomplexe über Kohlenwasserstoffbrücken
Authors: Beck Wolfgang , Bentele Hanns‐Jörg , Hüffer Stephan 
Published: July 2007

Addition of Hydrofulleride [C60H]− to Coordinated, Unsaturated Hydrocarbons: Binding of Fullerene to Metal Complexes through Hydrocarbon BridgesHerrn Professor Herbert Walter Roesky zum 60. Geburtstag gewidmet.
Hydrofulleride [C60H]− is added to the hydrocarbon ligands of the cationic complexes [(OC)5Re(η2‐C2H4)]+, [(OC)3Mn‐(η6‐C6H6)]+, [(OC)3M(η5‐C6H7)]+ (M = Fe, Ru), [(OC)3Fe(η5‐C7H9)]+, and [(η5‐C5H5)Fe(η6‐C5H4CH2)]+.
LiClO4‐Promoted Addition of Alkyl Grignard and Alkynyllithium Reagents to Ketones. Comparison of a 5 M LiClO4/Diethyl Ether Solution with CeCl3
Authors: Ipaktschi Junes , Eckert Thomas 
Published: July 2007

AbstractThe influence of a 5 M ethereal LiClO4 solution as solvent on the addition of different alkyl Grignard and alkynyllithium reagents to highly enolizable ketones was studied. A comparison with the results in the presence of CeCl3 shows a similar improvement in the yield.
Ylidylphosphorsulfide, ‐selenide, ‐disulfide, ‐sulfidselenide und ‐diselenide
Authors: Jochem Georg , Karaghiosoff Konstantin , Plank Stefan , Schmidpeter Stefan Dick Und Alfred 
Published: July 2007

Ylidylphosphorus Sulfides, Selenides, Disulfides, Sulfide Selenides, and DiselenidesWe report on the first stable monomeric phosphorus mono‐chalcogenides 2, 8 and the first stable dichalcogenides 4, 10 without bulky or intramolecularly coordinating substituents. They are stabilized by a high contribution of the zwitterionic resonance formula, which follows both from the NMR spectra and from an X‐ray structure determination. Their preparation starts from triphenylphosphoniumylidyl‐dichlorophosphanes 1. For the monochalcogenides they are treated with sodium sulfide or selenide or better with bis(trimethylsilyl) sulfide or selenide. In case of the C‐phenyl and C‐meta‐tolyl representatives and also of the C‐trimethylsilyl compound a number of secondary, partly novel products are obtained. – The dichalcogenides result from the reaction with sodium disulfide and diselenide, respectively, or from the oxidation of the monochalcogenides. – Alkylation of the monochalcogenides results in ylidylalkylchalcogenophosphenium salts 13, 15. In solution they are in equilibrium with more or less of the covalent form 14, 16, depending on the anion and on the solvent. Alkylation is often accompanied by secondary reactions. A diselenide loses selenium on alkylation.
Stabilization of a Planar‐tetracoordinate Carbon Center in an Organometallic Complex Containing Both a Zirconocene and a Hafnocene Moiety
Authors: Röttger Dirk , Erker Gerhard , Fröhlich Roland , Kotila Sirpa 
Published: July 2007

AbstractThe methylhafnocene cation 2a reacts with bispropynylzirco‐nocene to give a single regioisomeric planar‐tetracoordinate carbon compound (4a) that contains the hafnium atom singly‐bonded and the zirconium center η2‐coordinated to the bridging μ‐(η1‐C:η2‐C,C‐2‐butyne) ligand. However, the reaction between the methylzirconocene cation 2b with bis(phenylacetylide)hafnocene (3b) gives the pure regioiso‐mer 4b with an opposite relative arrangement of the two group 4 transition metals (the methyl is at the planar‐tetra‐coordinate carbon atom C2). Complex 4a was characterized by an X‐ray crystal structure analysis.