bluuebunny/crossref_metadata_2025_split huggingface dataset:
Multiple Functionalization of Bis(2‐pyridylimino)isoindole (BPI) Ligands: Their Modular Synthesis and Coordination to Palladium(II)
Authors: Siggelkow Bettina A. , Gade Lutz H. 
Published: October 2005

AbstractPolyether dendritic wedges have been attached to bis(2‐pyridylimino)isoindole (BPI) ligands, and the corresponding PdII complexes have been synthesized and studied as hydrogenation catalysts. The fixation of dendrons at the ligand framework was carried out at the stage of the phthalodinitrile precursor of the BPI ligands by nucleophilic substitution of 4‐nitrophthalodinitrile with the in situ generated alcoholates. Reaction of 1,3‐dibenzyloxy‐2‐propanol [G‐1] and the coupling of Fréchet's first and second generation arylether dendrons [(3,5)‐G‐1]‐OH, [t‐Bu‐(3,5)‐G‐1]‐OH and [(3,5)‐G‐2]‐OH with 4‐nitrophthalodinitrile gave the corresponding O‐coupled phthalodinitrile derivatives. The synthesis of the BPI ligands was achieved by reaction with two molar equivalents of 2‐amino‐5‐bromopyridine to give the protioligands (11‐Br)‐BPI‐[G‐1] (4) and (11‐Br)‐BPI‐[R‐(3,5)‐G‐1] (R = H: 5a, tBu: 5b) whereas the reaction of compound 5a with Me3SiCCH, Ph3SiCCH and PhCCH, using Sonogashira's [Pd(PPh3)4]/CuI catalyst, gave the corresponding bis(alkynyl)‐derivatives. All the protioligands were cleanly metallated to give the corresponding palladium(II) complexes. In contrast to the unsubstituted complex, its dendrimer functionalized derivatives [(11‐Br)‐BPI‐[R‐(3,5)‐G‐1]‐PdCl] (R = H: 9a, tBu : 9b) and [(11‐Br)‐BPI‐[(3,5)‐G‐2]‐PdCl] (11) hydrogenated styrene and 1‐octene without decomposition (TOF = 5 h−1 at T = 295 K, p(H2) = 1 bar, 2 mol% cat.) and among these, catalyst 11, carrying the 2nd generation dendron displayed sufficient stability to be isolated and reused several times.
Novel Hexacoordinate Diorganosilanes with Salen‐Type Ligands: Molecular Structure versus 29Si NMR Chemical Shifts
Authors: Wagler Jörg , Böhme Uwe , Brendler Erica , Blaurock Steffen , Roewer Gerhard 
Published: October 2005

AbstractStarting from diorganodichlorosilanes and the tetradentate salen‐type ligand 1 o‐HO‐p‐OMe‐C6H3‐C(Ph)=N‐(CH2)2‐N=C(Ph)‐C6H3‐p‐OMe‐o‐OH eight hexacoordinate diorganosilanes RR′Si[o‐O‐p‐OMe‐C6H3‐C(Ph)=N‐(CH2)2‐N=C(Ph)‐C6H3‐p‐OMe‐o‐O] [R, R′= Ph, Me (2a); Ph, Et (2b); Ph, Cy (2c); Vi, Me (2d); Ph, Vi (2e); Ph, Ph (2f); Me, Me (2g); ‐(CH2)3‐ (3)] were synthesized. In all these complexes the silicon atom is situated in a distorted octahedral coordination sphere. The organic substituents at the Si atom in 2a, 2b, 2e, 2f, and 2g are trans‐positioned. Referring to the almost planar coordination sphere provided by the tetradentate azomethine ligand in complexes 2a‐2g, the mer‐fac‐configuration, i.e. an all‐cis arrangement of the O, C and N donor atoms in 3, is especially remarkable. As proven by 29Si CP/MAS spectra as well as Si chemical shift tensor calculations, in compounds 2a, 2f and 2g the silicon atom is most shielded in the direction of the axially arranged Si‐C bonds.
Synthese, Kristallstruktur und magnetisches Verhalten von Gd(CF2HCOO)3(phen)
Authors: John Daniela , Urland Werner 
Published: October 2005

AbstractSynthesis, Crystal Structure, and Magnetic Behaviour of Gd(CF2HCOO)3(phen)Single crystals of Gd(CF2HCOO)3(phen) have been obtained by reaction of Gd(CF2HCOO)3(H2O)2·H2O with 1,10–phenanthroline in a solution of ethanol and water. The compound crystallizes in the triclinic space group $P{\bar 1}$ (Nr. 2, Z = 2, a = 874.6(2) pm, b = 928.9(1) pm, c = 1338.5(2) pm, α = 104.73°, β = 106.96°, γ = 99.92°). The Gd3+ ions are bridged by carboxylate groups to dimers and are ninefold coordinated by seven oxygen and two nitrogen atoms. The magnetic behaviour of the compound was investigated in the temperature range of 1.76 to 300 K. The magnetic data indicate an antiferromagnetic interaction within the dimeric unit (Jex = −0.016 cm−1).
Polyfluoroorganoboron‐Oxygen Compounds. 4 [1] Lithium Pentafluorophenyltrimethoxyborate, Li[C6F5B(OMe)3], Reactions with Selected Electrophiles and Nucleophiles
Authors: Adonin Nicolay Yu. , Bardin Vadim V. , Flörke Ulrich , Frohn Hermann‐Josef 
Published: October 2005

AbstractLi[C6F5B(OMe)3] (1a) reacted with the electrophiles CD3C(O)CD3, CH3OD, CD3CN, CH3CN, HOC2H4OH, Br2, and I2 to give C6F5X (X = D, H, Br, I). The treatment of 1a with Me3SiCl or BF3 in CH2Cl2 and CCl3F or pentene resulted in C6F5B(OMe)2 or C6F5BF2, respectively. The attempted metathesis of 1a with KF or [Bu4N]Br in CH2Cl2 led to a mixture of M[(C6F5)2B(OMe)2] (2b,c, main product) and M[C6F5B(OMe)3] (1b,c, minor product) (M = [Bu4N], K). Even in the presence of diethyl ether, THF, DME, or TMEDA salt 1a underwent dismutation to the diarylborate salt [Li(L)n][(C6F5)2B(OMe)2] (L = Et2O, THF, DME, TMEDA) and [Li(L)n][B(OMe)4]. In subsequent reactions with aqueous K[HF2] or [Bu4N][HF2] M[(C6F5)2B(OMe)2] (M = K, [Bu4N], [Li(L)n]) yielded K[(C6F5)2BF2] (4c) or [Bu4N][(C6F5)2BF2] (4b). The molecular structure of [Li·TMEDA][(C6F5)2B(OMe)2] from single crystals showed significant cation‐oxygen interactions.
Reactivity of Rhenium Complexes Containing a Triamidoamine Ligand Toward Samarium Diiodide
Authors: Mösch‐Zanetti Nadia C. , Magull Jörg 
Published: October 2005

AbstractThe reaction of [(HN3N)ReOCl] (1) that contains the unsymmetric tren‐based ligand HN3N = ({C6F5NCH2CH2}2NCH2CH2CH2NHC6F5)2− with samarium diiodide leads to the formation of the iodide compounds [(N3N)ReI] (2) and [(HN3N)ReOI] (3). The reduction reaction also generates the unusual rhenium(IV) compound [(HN3N*)ReX] (4, X = 0.35 % F and 0.65 % I,), where the amine ligand HN3N* = ({C6F5NCH2CH2}2NCH2CH2CH2NHC6F4)3− is involved in an intramolecular C‐F bond activation. The larger 6‐membered metallacycle formed by the propylene amido substituent facilitates ortho metallation. All compounds have been characterized by single crystal X‐ray analyses.
Synthesis and Structure of a Novel Type of Polyoxomolybdate Lanthanide Complex: [(Ln(H2O)6)2(TeMo6O24)] (Ln = Ho, Yb)
Authors: Drewes Daniel , Krebs Bernt 
Published: October 2005

AbstractThe new polyoxomolybdates [(Ho(H2O)6)2(TeMo6O24)] · 10 H2O (1) and [(Yb(H2O)6)2(TeMo6O24)] · 10 H2O (2) were prepared from aqueous solution by reaction of telluric acid, potassium molybdate and holmium chloride and ytterbium chloride, respectively. They were characterized by X‐ray structure analysis, energy dispersive X‐ray fluorescence analysis and IR spectroscopy. Both compounds contain the Anderson type anion (TeMo6O24)6− and trivalent lanthanide atoms which achieve eightfold coordination by two terminal oxygen atoms of the (TeMo6O24)6− anion and six crystal water molecules. While all known Ln/(TeMo6O24)6− compounds contain infinite one‐dimensional chains in which the (TeMo6O24)6− anions are linked by rare earth cations, the neutral molecular [(Ln(H2O)6)2(TeMo6O24)] complexes in 1 and 2 are only connected via hydrogen bonds.
Multifunctional Phosphorus Compounds: Molecular Structures of 1,2,4,5‐Tetra(phosphinyl)‐, Tetra(dimethoxyphosphoryl)‐, and Tetra(dihydroxyphosphoryl)benzene
Authors: Reiter Stephan A. , Nogai Stefan D. , Schmidbaur Hubert 
Published: October 2005

Abstract1,2,4,5‐Tetra(phosphinyl)benzene (1) and ‐tetrakis(dimethoxyphosphoryl)benzene (4) have molecular structures of point group Ci symmetry with conformations largely determined by steric factors. In the crystal of compound 1 there are no discernible effects of intra‐ or intermolecular P–H···P hydrogen bonding. By contrast, the crystal structure of the corresponding phosphonic acid, 1,2,4,5‐tetrakis(dihydroxyphosphoryl)benzene (3), is governed by a network of hydrogen bonds between PO(OH)2 groups with monofunctional P–OH donors and difunctional P=O acceptors as required for a maximum set of hydrogen bonds under the given stoichiometry. The aggregation of the molecules (Ci symmetry) leads to narrow channels formed by 14‐ and 16‐membered rings which comprise POH···OP bridges between P–CC–P and P–CCC–P units, respectively. Accordingly, the crystals of compound 3 are mechanically extremely robust. A tri(phosphinyl)benzene (2) with an interesting 1,2,4‐ substitution pattern has been obtained as a by‐product of the synthesis of the tetra(phosphinyl)benzene (1) where it is formed by reductive P–C cleavage.
Some Investigations on Organotellurium(IV) Cyanides
Authors: Klapötke Thomas M. , Krumm Burkhard , Mayer Peter , Polborn Kurt , Schwab Ingo 
Published: October 2005

AbstractFluorination of R2Te (R = 2,4,6‐Me3C6H2 (= Mes) (1), 2,4,6‐iPr3C6H2 (= Trip) (2)) with xenon difluoride afforded the sterically demanding diorganotellurium(IV) difluorides R2TeF2. The reaction of R2TeF2 (R = Me, Ph, Mes (3), Trip (4)) with trimethylsilyl cyanide resulted in the formation of either R2Te(CN)2 (R = Ph (5), Mes (6)) or the monotellanes R2Te (R = Me, Trip). Upon reaction of Mes2TeF2 (3) with trimethylsilyl azide, dimesityltellurium(IV) diazide Mes2Te(N3)2 (8) was prepared. Characterization by standard methods has been carried out, and in addition, the crystal structures of 1, 3, and (Mes2TeCN)2O (7) were determined, the latter being the first organotellurium(IV) cyanide for which structural information is available.
Atrane and Phosphorane Formation with Aminotriphenols [1]
Authors: Timosheva Natalya V. , Chandrasekaran A. , Holmes Robert R. 
Published: October 2005

AbstractReaction of the aminotriphenol, tris (2‐hydroxy‐3‐methyl‐5‐tert‐butylbenzyl)amine, with triphenylphosphite resulted in the formation of the first structurally characterized pentaoxyphosphorane‐atrane, N[CH2(Me(t‐Bu)C6H2)O]3P(OPh)2 (1) while reaction of the aminotriphenol, tris (2‐hydroxy‐3,5‐dimethylbenzyl)amine (E) with 2,2′ethylidenebis(4,6‐di‐tert‐butylphenyl)fluorophosphite led to the isolation of the phosphorane, N[CH2(Me2C6H2)O]2P[OC6H2(t‐Bu)2]2CHCH3 (2), as a result of aminotriphenol to aminodiphenol conversion. X‐ray analysis revealed the octahedral geometry of 1 showing strong P‐N dative bond coordination (2.114(6) Å) and the trigonal bipyramidal arrangement for 2 exhibiting a normal P‐N covalent bond (1.652(2) Å). 1H, 13C and 31P NMR measurements assisted in the structural interpretations and in comparisons with related compounds. The results confirm the premise that donor action at the transition state of active sites of phosphoryl transfer enzymes should enjoy enhanced reaction with nearby donor groups that are positioned to enter into coordination with the reactive phosphoryl component, especially for such enzymatic reactions that exhibit catalytic promiscuity.
Synthesis and Structures of Zeise‐type Complexes with Vinylsilane Ligands and Quantum Chemical Analysis of the Platinum–Vinylsilane Bonding
Authors: Schwieger Sebastian , Wagner Christoph , Bruhn Clemens , Schmidt Harry , Steinborn Dirk 
Published: October 2005

AbstractZeise‐type complexes with vinylsilanes as π‐ligands [K(18C6)][PtCl3(η2‐CH2=CHX)] (X = SiMe3, 4; SiPh3, 5; Si(OMe)3, 6; 18C6 = 18‐crown‐6) and [K(18C6)]2[(PtCl3)2{η2,η2‐(CH2=CHSiMe2)2O}] (7) have been prepared by the reaction of [K(18C6)]2[Pt2Cl6] (3) with the appropriate vinylsilanes. The identities of the complexes have been confirmed by NMR spectroscopy as well as for 4, 5 and (PPh4)[PtCl3{η2‐CH2=CHSi(OMe)3}] (6′) also by single‐crystal X‐ray diffraction measurements. DFT calculations exhibited, that the coordination induced C=C bond lengthenings and the pyramidalization angles of the olefins in the vinylsilane complexes [PtCl3(η2‐CH2=CHX)]− (X = SiMe3, 4c; SiPh3, 5c; Si(OMe)3, 6c) are the same as in Zeise's anion [PtCl3(η2‐CH2=CH2)]− (8c) while the amount of the π back‐donation in the vinylsilane complexes 4c–6c is higher than that in the ethylene complex 8c.
Coordination Polymers of Iron(III) and (II) with 4,4′‐Bipyridine: Hydrothermal Syntheses, Structures, Absorption and Mössbauer Studies Showing Spin Crossover for the Iron(III) Polymer
Authors: Abu‐Shandi Khalid , Winkler Heiner , Paulsen Hauke , Glaum Robert , Wu Biao , Janiak Christoph 
Published: October 2005

AbstractThe iron‐4,4′‐bipyridine coordination polymers $^{1}_{\infty}\rm\{[Fe^{III}(NO_{3})_{2}({\rm \mu}-4,4^{\prime}-bipy)(H_{2}O)_{2}]OH\cdot H_{2}O\}$ (1) and $^{1}_{\infty}\rm\{[Fe^{II}(H_{2}PO_{4})_{2}({\rm \mu}-4,4^{\prime}-bipy)(H_{2}O)]\cdot H_{2}O\cdot (4,4^{\prime}-bipy)\}$ (2) have been synthesized by hydrothermal methods. The structure of 1 is a channel‐containing open framework constructed through the hydrogen‐bond supported criss‐cross arrangement of the 1D Fe‐bipy chains. 57Fe Mössbauer spectroscopy reveals a gradual spin crossover behavior for 1 with a magnetic ordering at low temperature. The structure of 2 is constructed from parallel oriented, hydrogen‐bonded 1D Fe‐bipy chains. The 4,4′‐bipyridine solvate in 2 is held by hydrogen bonding between the H2PO4 groups on adjacent iron centers along the chain and is situated in a π–π stacking contact to the coordinated 4,4′‐bipy ligand. The chains in 2 are interconnected through hydrogen bonding to a three‐dimensional supramolecular network. Crystals of 2 appear dark red or orange depending on the orientation (pleochroism, dichroism).
Carbonylnitrosylrhenium‐Komplexe mit α‐Aminosäureester‐Liganden [1]
Authors: Urban Reinhold , Veghini Dario , Berke Heinz , Beck Wolfgang 
Published: October 2005

AbstractCarbonylnitrosylrhenium Complexes with α‐Amino Acid Ester Ligands [1]The reaction of the chloro bridged [Re(Cl)(μ‐Cl)(CO)2(NO)]2 with acetonitrile gives [ReCl2(CO)2(NO)(CH3CN)] (1) which was used as starting complex for the synthesis of the α‐amino acid ester complexes [ReCl2(CO)2(NO)(NH2CHRCO2R′)] (2‐5; R = H, Me, CHMe2, Ch2Ph; R′ = Et, Me). Similarly, THF in [ReCl2(CO)2(NO)(THF)] can be substituted by R(+)‐1‐phenylethylamine with formation of 6. From the formation of two diastereoisomers of 3‐6 the structure of the chiral complexes [ReCl2(CO)2(NO)L] can be elucidated.
Übergangsmetallorganische Reaktionskaskaden zum Aufbau höher aggregierter Systeme: Nickelacyclische Carboxylate als Precursoren für die Synthese eines Oxinato‐Nickel(II)‐Tetramers
Authors: Langer Jens , Görls Helmar , Gillies Glenn , Walther Dirk 
Published: October 2005

AbstractOrgano Transition Metal Cascade Reactions for Forming Higher Aggregeted Systems: Nickelacyclic Carboxylates as Precursors for the Synthesis of a Oxinato‐Nickel(II)‐TetramerDiisopropyl‐8‐oxychinolylphosphinite (2) reacts with the nickelacycle [(py)2Ni‐CH2CH2‐COO] under formation of the thermically stable nickelalactones [(2)Ni‐CH2CH2‐COO] (4) the solid state structure of which was determined by an X‐ray crystallographic analysis. In 4 the ligand acts as a six‐membered chelating ligand with P,N coordination. According to the NMR spectrathis structure is present in solution as well. However, the stronger electron‐withdrawing diphenyl‐8‐0xychinolylphosphinite reacts under similar conditions in further reactions yielding the tetranuclear oxinato‐diphenylphosphinato‐Ni(II) complex 6 in the presence of oxygen. The structure of 6 was determined by an X‐ray analysis. The formation of 6 is the result of a reaction cascade of at least five metal‐assisted reactions which occur step by step, and to some extend in parallel reactions.
Bis(trifluoromethylselenato(0))metallates(I) of Silver and Gold, [M(SeCF3)2]− (M = Ag, Au)
Authors: Naumann Dieter , Tyrra Wieland , Quadt Silke , Buslei Sigrid , Pantenburg Ingo , Schäfer Mathias 
Published: October 2005

AbstractLigand exchange reactions of [NMe4]SeCF3 or [Cs(15‐Crown‐5)2]SeCF3 with Ag[BF4] and AuCl gave the corresponding bis(trifluoromethylselenato(0))metallates [Ag(SeCF3)2]‐ and [Au(SeCF3)2]‐ in good yields. All compounds were characterized by NMR spectroscopic means and ESI mass spectrometry. Cation exchange with [PNP]Cl ([PNP] = bis(triphenylphosphoranylidene)ammonium) yielded the corresponding [PNP] salts. The single crystal structure of [PNP][Au(SeCF3)2] was elucidated by XRD measurements (P21/a; a = 1712.0(1), b = 1142.5(1), c = 2013.6(1) pm; β = 112.10(1)°; Z = 4).
Synthesis and Characterization of Et2NM{OB[OSi(OtBu)3]2}3 (M = Zr, Hf) Molecular Precursors to Zr/B/Si/O and Hf/B/Si/O Materials
Authors: Fujdala Kyle L. , Tilley T. Don 
Published: October 2005

AbstractTwo new transition metal complexes containing the –OB[OSi(OtBu)3]2 ligand, Et2NM{OB[OSi(OtBu)3]2}3 (M = Zr, Hf), are reported. These species are the 4th and 5th examples of complexes containing this recently reported borosiloxide ligand. Their use as potential molecular precursors to multi‐component oxide materials via the thermolytic molecular precursor (TMP) method is discussed.
Ambient‐Condition nano‐Alumina Formation Through Molecular Control
Authors: Wang Yuzhong , Bhandari Sonali , Mitra Amitabha , Parkin Sean , Moore Jerry , Atwood David A. 
Published: October 2005

AbstractWhen toluene solutions of the tetrametallic compound, [Al{μ‐OEt)2AlMe2}3] (1), are stirred in air at room temperature, pure amorphous nanoparticulate Al2O3 precipitates. The average particle size is 17.7 ± 7.4 nm. The tetrametallic core of 1, having the correct stoichiometry for alumina (2Al2O3) appears to act as a template or nucleating site for the formation of alumina rather than the expected products of formula, AlOOH. The stability of the Al4O6 core of 1 was tested by combining it with six equivalents of Ph3SiOH. This resulted in [Al{μ‐OEt)2Al(OSiPh3)2}3] (2). Upon exposure to air, compound 2 formed the hydroxide derivative [Al{μ‐OH)2Al(OSiPh3)2}3] (3). This demonstrates that the tetrametallic core of 1 is stable to both peripheral derivatization as well as alcoholysis of the internal bridging groups.
Coordination Chemistry of Acrylamide 2. Classical Complexes of Acrylamide with Manganese(II), Iron(II) and Nickel(II) Chlorides: Syntheses and Crystal Structures
Authors: Girma K. B. , Lorenz Volker , Blaurock Steffen , Edelmann Frank T. 
Published: October 2005

AbstractMetal complexes of manganese(II), iron(II), and nickel(II) chlorides with acrylamide, [M(O‐OC(NH2)CH=CH2)4Cl2] (M = Mn (1), Fe (2) and Ni (3)), have been prepared and characterized by single crystal X‐ray diffraction, IR spectroscopy and elemental analyses. The complexes crystallize in the cubic space group, ${\rm I}{\bar 4}{\rm 3d}$. The coordination geometries of the metal centers in all three complexes involve tetragonally distorted octahedral structures with four O‐donor atoms of acrylamide bonded in the equatorial positions and two chlorides in the apical positions.
New Phenylnickel‐(2‐phosphinobenzenesulfonate) Triphenylphosphine Complexes as Highly Active Ethylene Polymerization Catalysts
Authors: Nowack Rüdiger J. , Hearley Andrew K. , Rieger Bernhard 
Published: October 2005

AbstractThe first examples of SHOP type nickel(II) catalysts bearing new phosphine chelate ligands comprised of a coordinating sulfonate functional group have been synthesized and structurally characterized. These catalysts show high activities in the polymerization of ethylene and can even be used without phosphine scavengers. Polyethylenes with 15–25 branches per 1000 carbon atoms are produced from ethylene monomer alone.
Strong Electronic Coupling between Mo2n+ Units: The Oxidation Products of [Mo2(DAniF)3]2(μ−H)2 and Mo2(DAniF)4
Authors: Cotton F. Albert , Donahue James P. , Huang Penglin , Murillo Carlos A. , Villagrán Dino 
Published: October 2005

AbstractThe two compounds [[Mo2(DAniF)3]2(μ−H)2]PF6 (2), and [Mo2(DAniF)4]TFPB (3), (DAniF represents (p−MeOC6H4N)2CH, and TFPB tetra–3,5–bis(trifluoromethyl)phenylborate) have been prepared and characterized structurally by X‐ray crystallography, and by cyclic voltammetry and EPR spectroscopy. DFT calculations have been performed on 2. This is a fully delocalized system in which the two Mo2 units have essentially identical Mo–Mo distances, 2.115(1) Å and 2.116(1) Å, that are 0.017(1) Å longer than those in the neutral precursor. Delocalization over four molybdenum atoms is confirmed by the hyperfine structure observed in the EPR spectrum. No coupling of the delocalized electron to the bridging protons is observed, and this is consistent with the electronic structure calculated by DFT. The cation in 3, which is commonly a contaminant of 2, shows exactly the structural and EPR characteristics expected.
Synthesis and Structural Characterization of a Series of Tetranuclear Lanthanide Clusters
Authors: Baskar Viswanathan , Roesky Peter W. 
Published: October 2005

AbstractTetranuclear lanthanide clusters of composition [Ln4(μ3‐OH)2(Ph2acac)10] (Ln = Pr, Nd, and Sm) (Ph2acac = dibenzoylmethanide) were prepared starting from [LnCl3·(n H2O)] (n = 6, 7) with 2.5 equivalents dibenzoylmethane in presence of triethylamine. Single crystals X‐ray analyses of compounds 1 ‐ 3 revealed that each cluster consists of four lanthanide atoms, two μ3‐oxygen atoms, and ten Ph2acac ligands, which make up the peripheral part of the cluster. Three types of coordination modes (η2‐, (μ‐O)‐η2‐, and μ‐O)2‐η2) are observed for the Ph2acac ligation to the metal centers.
nBu3P‐Silber(I)‐β‐Diketonate: Synthese, Gasphasenuntersuchungen und Verwendung als CVD‐Precursoren
Authors: Schmidt H. , Jakob A. , Haase T. , Kohse‐Höinghaus K. , Schulz S. E. , Wächtler T. , Gessner T. , Lang H. 
Published: October 2005

AbstractnBu3P‐Silver(I)‐β‐Diketonates: Synthesis, Gas Phase Studies, and their Use as CVD‐PrecursorsThe synthesis of the silver(I) salts [AgX] (3a, X = acetylacetonate, acac; 3b, X = 1,1,1,5,5,5‐hexafluoroacetylacetonate, hfac; 3c, X = 1,3‐diphenyl‐1,3‐propanedionate, dipa) by the reaction of [AgNO3] (1) with H‐X (2a, X = acac; 2b, X = hfac; 2c, X = dipa), or [Ag2O] (4) with 2b is reported. The addition of nBu3P (5) to 3a ‐ 3c in the ratios of 1:1 and 2:1, respectively, affords the phosphane silver(I) β‐diketonates [(nBu3P)mAgX] (m = 1: 6a, X = acac; 6b, X = hfac; 6c, X = dipa. m = 2: 7a, X = acac; 7b, X = hfac; 7c, X = dipa) in excellent yield.The thermal behaviour (thermogravimetry) and gas phase properties (temperature‐programmed mass spectrometry) of selected species are discussed.Complex 7a can successfully be used in the deposition of silver on titanium nitride coated oxidized silicon wafers by the CVD process (CVD = Chemical Vapour Deposition). SEM studies show that homogeneous and continuous silver layers were obtained.
Synthesis and Characterization of Au55 Clusters within Mesoporous Silica
Authors: Lotz Andreas R. , Fröba Michael 
Published: October 2005

AbstractThe cluster compound Au55(PPh3)12Cl6 was synthesized via the reduction of (triphenylphosphine)gold chloride with diborane and incorporated into the mesopores of SBA‐15 silica. As alternative pathway, the synthesis of Au55 clusters directly within the silica matrix was investigated. Remarkably, the comparison of the two different methods shows that incorporation of the preformed clusters and intra‐pore synthesis give nearly identical products. Powder X‐ray diffractometry and nitrogen physisorption clearly prove the preservation of the mesoporous host matrix and the filling of the pores. Transmission electron microscopy studies reveal that the individual clusters are preferentially located inside the pore system, bulk formation on the outer surface is not observed. The guest species can partially be dissolved out of the host matrix by dichloromethane. Annealing of the host/guest compound leads to decomposition of Au55(PPh3)12Cl6 to metallic gold within the pores, whereas the particle size increases with rising temperature.