- Tris(mercaptoimidazolyl)borate complexes of the coinage metals: Syntheses and molecular structures of the first gold compounds and related copper and silver derivatives
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The first tris(mercaptoimidazolyl)borate complexes of gold, Au(Tm tBu) and (TmtBu)Au(PPh3), have been prepared and structurally characterized. Together with their copper and silver analogues M(TmtBu) and (Tmsup
- Patel, Denish V.,Mihalcik, David J.,Kreisel, Kevin A.,Yap, Glenn P. A.,Zakharov, Lev N.,Kassel, W. Scott,Rheingold, Arnold L.,Rabinovich, Daniel
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- Hierarchy of Supramolecular Arrangements and Building Blocks: Inverted Paradigm of Crystal Engineering in the Unprecedented Metal Coordination of Methylene Blue
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The aromatic methylene blue cation (MB+) shows unprecedented ligand behavior in the X-ray structures of the trigonal-planar (TP) complexes MBMCl2 (M = CuI, AgI). The two isostructural compounds were exclusively synthesized by grinding together methylene blue chloride and MCl solids. Only in the case of AuCl did the technique lead to a different, yet isoformular, AuI derivative with separated MB+ and AuCl2- counterions and no direct N-Au linkage. While the density functional theory (DFT) molecular modeling failed in reproducing the isolated Cu and Ag complexes, the solid-state program CRYSTAL satisfactorily provided for Cu the correct TP building block associated with a highly compact π stacking of the MB+ ligands. In this respect, the dispersion interactions, evaluated with the DFT functional, provide to the system an extra energy, which likely supports the unprecedented metal coordination of the MB+ cation. The feature seems governed by subtle chemical factors, such as, for instance, the selected metal ion of the coinage triad. Thus, the electronically consistent AuI ion does not form the analogous TP building block because of a looser supramolecular arrangement. In conclusion, while a given crystalline design is generally fixed by the nature of the building block, a peculiarly efficient supramolecular packing may stabilize an otherwise unattainable metal complex.
- Canossa, Stefano,Bacchi, Alessia,Graiff, Claudia,Pelagatti, Paolo,Predieri, Giovanni,Ienco, Andrea,Manca, Gabriele,Mealli, Carlo
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- Bright Luminescence in Three Phases—A Combined Synthetic, Spectroscopic and Theoretical Approach
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Combining phase-dependent photoluminescence (PL) measurements and quantum chemical calculations is a powerful approach to help understand the influence of the molecular surroundings on the PL properties. Herein, a phosphine functionalized amidinate was used to synthesize a recently presented bimetallic gold complex, featuring an unusual charge separation. The latter was subsequently used as metalloligand to yield heterotetrametallic complexes with an Au-M-M-Au “molecular wire” arrangement (M=Cu, Ag, Au) featuring metallophilic interactions. All compounds show bright phosphorescence in the solid state, also at ambient temperature. The effect of the molecular environment on the PL was studied in detail for these tetrametallic complexes by comparative measurements in solution, in the solid state and in the gas phase and contrasted to time-dependent density functional theory computations.
- Dahlen, Milena,Gamer, Michael T.,Hollesen, Eike H.,Kappes, Manfred M.,Kehry, Max,Klopper, Wim,Lebedkin, Sergei,Roesky, Peter W.,Schooss, Detlef
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- Preparation of an organometallic molecular square by self-assembly of phosphorus-containing building blocks
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Molecular squares are among the most common supramolecular architectures, but phospha-organometallic complexes have not been used as building blocks for this type of structure. Herein we describe the formation of the molecular square [Au{Co(P2C2tBu2)2}]4 (1) by the self-assembly of anionic 1,3-diphosphacyclobutadiene cobalt complexes and gold(I) cations. The X-ray crystallographic determination of the molecular structure of 1 is complemented by solid-state 31P and 13C NMR investigations. High-level DFT calculations confirm the assignment of the 31P and 13C NMR resonances. A square of gold: [Au{Co(P2C2tBu2)2}]4 is formed by the self-assembly of gold(I) cations and anions comprising a cobalt center sandwiched by phosphorus-containing moieties. X-ray diffraction and NMR spectroscopy investigations confirm that the metal atoms form a C4 symmetrical arrangement. The results show the potential of phospha- organometallic sandwich complexes as building blocks in supramolecular assemblies.
- Malberg, Jennifer,Bodensteiner, Michael,Paul, Daniel,Wiegand, Thomas,Eckert, Hellmut,Wolf, Robert
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- Organometallic complexes for non-linear optics XII. Syntheses and second-order susceptibilities of (neomenthyldiphenylphosphine) gold σ-arylacetylides: X-ray crystal structures of Au( C≡CPh) (nmdpp) and Au((E)-4,4′-C≡CC6H4CH=CHC6H4NO2)(nmdpp)
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The series of complexes Au(C≡CR)(nmdpp) (R = Ph (2), 4-C6H4NO2 (3), 4,4′-C6H4C6H4NO2 (4), (Ε)-4,4′-C6H4CH=CHC6H4NO2 (5), (Ζ)-4,4′-C6H4CH=CHC6H4NO2 (6), 4,4′-C6H4C≡CC6H4NO2 (7), 4,4′-C6H4N=CHC6H4NO2 (8); nmdpp = (+)-neomenthyldiphenylphosphine) has been synthesized by reaction of AuCl(nmdpp) with the corresponding acetylene and methoxide in the presence of trace amounts of a phosphine oxide, and complexes 2 and 5 have been structurally characterized. Complexes 2-8 and analogous (triphenylphosphine)gold acetylides and precursor (phosphine)gold chlorides have been examined for their second-order bulk susceptibilities χ(2) by the Kurtz powder technique, with the largest response (ca. 2 × urea) being that from 3.
- Whittall, Ian R.,Humphrey, Mark G.,Samoc, Marek,Luther-Davies, Barry,Hockless, David C.R.
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- Bi- And trinuclear coinage metal complexes of a PNNP ligand featuring metallophilic interactions and an unusual charge separation
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A selective synthesis of bi- and trinuclear complexes featuring a tetradentate monoanionic PNNP ligand is presented. The binuclear coinage metal complexes show a typical fourfold coordination for Cu and Ag, which changes to a bifold coordination for Au. The latter is accompanied by an unusual charge separation. Optical properties are investigated using photoluminescence spectroscopy and complemented by time-dependent density-functional-theory calculations. All compounds demonstrate clearly distinguished features dependent on the metals chosen and differences in the complex scaffold.
- Dahlen, Milena,Kappes, Manfred M.,Kehry, Max,Klopper, Wim,Lebedkin, Sergei,Roesky, Peter W.
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supporting information
p. 13412 - 13420
(2021/10/12)
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- Metal-to-Metal Distance Modulated Au(I)/Ru(II) Cyclophanyl Complexes: Cooperative Effects in Photoredox Catalysis
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The modular synthesis of Au(I)/Ru(II) decorated mono- and heterobimetallic complexes with π-conjugated [2.2]paracyclophane is described. [2.2]Paracyclophane serves as a rigid spacer which holds the metal centers in precise spatial orientations and allows
- Bizzarri, Claudia,Br?se, Stefan,Diller, Rolf,Hassan, Zahid,Israil, Roumany,Kappes, Manfred M.,Nieger, Martin,Riehn, Christoph,Schüssler, Lars,Schneider, Erik K.,Weis, Patrick,Zippel, Christoph
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supporting information
p. 15187 - 15200
(2021/11/01)
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- A Macrocyclic Gold(I)–Biphenylene Complex: Triangular Molecular Structure with Twisted Au2(diphosphine) Corners and Reductive Elimination of [6]Cycloparaphenylene
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The digold(I) complex [Au2Cl2(Cy2PCH2PCy2)] reacts with 4,4′-diphenylene diboronic acid to form a triangular macrocyclic complex with twisted Au-P-C-P-Au groups at the three corners. The synthesis of
- Abe, Ryota,Ide, Tomohito,Osakada, Kohtaro,Tsuchido, Yoshitaka
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supporting information
p. 22928 - 22932
(2020/09/02)
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- Gold(I)-Catalysed Hydroarylation of Lactam-Derived Enynes as an Entry to Tetrahydrobenzo[g]quinolines
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The gold(I)-catalysed cyclization of N-tosyl-protected 5-benzyl-6-((trimethylsilyl)ethynyl)-1,2,3,4-tetrahydropyridines, prepared by the Sonogashira coupling of lactam-derived enol triflates, provides tetrahydrobenzo[g]quinolines whose skeleton represents a recurrent motif in natural compounds. The Au(I)-catalysed reaction is carried out with (C6F5)3PAuCl/AgNTf2 as the catalyst system and proceeds via a 6-exo-dig cyclization to form an exocyclic double bond, which eventually isomerises to the aromatic tetrahydrobenzo[g]quinoline. The mode of cyclization is discussed and supported by DFT calculations.
- Nejrotti, Stefano,Ghinato, Simone,Gini, Elena C.,Scarpi, Dina,Occhiato, Ernesto G.,Maranzana, Andrea,Prandi, Cristina
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supporting information
p. 646 - 653
(2019/12/27)
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- Exploring the self-assembled tacticity in aurophilic polymeric arrangements of diphosphanegold(I) fluorothiolates
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Despite the recurrence of aurophilic interactions in the solid-state structures of gold(I) compounds, its rational control, modulation, and application in the generation of functional supramolecular structures is an area that requires further development.
- Moreno-Alcántar, Guillermo,Salazar, Laura,Romo-Islas, Guillermo,Flores-álamo, Marcos,Torrens, Hugo
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- Selective Synthesis of ortho-Substituted Diarylsulfones by Using NHC-Au Catalysts under Mild Conditions
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A single-step gold(I)-catalyzed chemoselective protocol to access ortho-substituted diarylsulfones has been established. Acenaphthoimidazolylidene gold complexes are effective catalysts for the arylsulfonylation of boronic acids by potassium metabisulfite (K2S2O5) and diaryliodonium salts to access (poly-)ortho-substituted diarylsulfones even in gram scale. Unlike the transition metal-catalyzed two-component coupling systems, the sterically hindered aryl groups in diaryliodonium salts are preferentially transferred over less bulky ones to form synthetically difficult targets, including those of pharmaceutical importance.
- Zhu, Haibo,Shen, Yajing,Wen, Daheng,Le, Zhang-Gao,Tu, Tao
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supporting information
p. 974 - 979
(2019/02/14)
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- Highly efficient aggregation-induced room-temperature phosphorescence with extremely large Stokes shift emitted from trinuclear gold(I) complex crystals
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Highly efficient (≈75% quantum yield), aggregation-induced phosphorescence is reported. The phosphorescence is emitted at room temperature and in the presence of air from crystals of trinuclear Au(I) complexes, accompanied by an extremely large Stokes shift of 2.2 × 104 cm?1 (450 nm). The mechanism of the aggregation-induced room-temperature phosphorescence from the Au complex crystals was investigated in terms of the crystal packing structure and the primary structure of the molecules. It was found that two kinds of intermolecular interactions occurred in the crystals, and that these multiple dual-mode intermolecular interactions in the crystals play a crucial role in the in-air room-temperature phosphorescence of the trinuclear Au(I) complexes.
- Tsutsumi, Osamu,Tamaru, Masakazu,Nakasato, Hitoya,Shimai, Shingo,Panthai, Supattra,Kuroda, Yuki,Yamaguchi, Kenta,Fujisawa, Kaori,Hisano, Kyohei
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supporting information
(2019/12/25)
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- The Energetic Significance of Metallophilic Interactions
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Metallophilic interactions are increasingly recognized as playing an important role in molecular assembly, catalysis, and bio-imaging. However, present knowledge of these interactions is largely derived from solid-state structures and gas-phase computatio
- Zheng, Qingshu,Borsley, Stefan,Nichol, Gary S.,Duarte, Fernanda,Cockroft, Scott L.
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supporting information
p. 12617 - 12623
(2019/08/12)
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- Single-Molecule Observation of the Intermediates in a Catalytic Cycle
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The development of catalysts benefits from knowledge of the intermediate steps that accelerate the transformations of substrates into products. However, key transient species are often hidden in ensemble measurements. Here, we show that a protein nanoreac
- Ramsay, William J.,Bell, Nicholas A. W.,Qing, Yujia,Bayley, Hagan
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supporting information
p. 17538 - 17546
(2019/01/04)
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- Oxidative 1,2-Difunctionalization of Ethylene via Gold-Catalyzed Oxyarylation
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Under the conditions of oxidative gold catalysis, exposure of ethylene to aryl silanes and alcohols generates products of 1,2-oxyarylation. This provides a rare example of a process that allows catalytic differential 1,2-difunctionalization of this feedstock chemical.
- Harper, Matthew J.,Emmett, Edward J.,Bower, John F.,Russell, Christopher A.
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supporting information
p. 12386 - 12389
(2017/09/22)
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- Some insights into the gold-catalysed A3-coupling reaction
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A series of cyclometallated and functionalised NHC gold(I) and gold(III) complexes, many of which feature chiral ligands, and their application to A3-coupling reactions is presented. Gold(III) complexes were found to be particularly effective catalysts for the coupling in a range of solvents, however no asymmetric induction was obtained when using chiral gold complexes and the rate of product formation was found to be similar even when using different ligand systems. In-situ NMR analysis of these reactions indicates that decomposition of the catalyst occurs during the course of the reaction while TEM studies revealed the presence of gold nanoparticles in crude reaction mixtures. Taken together these data suggest that the gold nanoparticles, rather than the intact gold complexes, could be the catalytically active species, and if so this may have significant implications for other gold-catalysed systems.
- Price, Gregory A.,Brisdon, Alan K.,Randall, Simon,Lewis, Edward,Whittaker, Daniel M.,Pritchard, Robin G.,Muryn, Chris A.,Flower, Kevin R.,Quayle, Peter
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supporting information
p. 251 - 262
(2017/07/06)
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- A substituted bay position gold[...] imide derivatives (by machine translation)
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A substituted bay position gold[...] imide derivatives, its chemical formula is R 2-PDI-R 1, the structural formula , In the formula: derivatives in PDI-a R 1 to PPh 3, R 2 to H; derivative compound in PDI-b R 1 to PPh 3, R 2 to Au-PPh 3; in PDI-b the derivation gathers the thing R1 to C ≡ N-Ph, R 2 to H. Substituted position goldstates the bay[...] the preparation process of imide derivative, the steps are as follows : (1) synthesis of diamide derivatives perylen ; (2) synthesis of gold-containing derivatives. The advantage of this invention is: the method of preparing substituted bay position gold[...] imide derivatives, fluorescent obviously enhance and stable properties, good heat conducting properties, in aviation and aerospace, photoelectric. Many machinery and the like, and have a wide range of application prospect. (by machine translation)
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Paragraph 0030; 0053
(2017/02/09)
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- Room-Temperature Hydration of Alkynes Catalyzed by Different Carbene Gold Complexes and their Precursors
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The room-temperature hydration of alkynes catalyzed by NHC-gold(I) (NHC=N-heterocyclic carbene), NAC-gold(I) (NAC=nitrogen acyclic carbene), and isocyanide gold(I) complexes was investigated carefully in the presence of different weakly coordinating anion
- Xu, Yun,Hu, Xingbang,Zhang, Shufeng,Xi, Xiuxing,Wu, Youting
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p. 262 - 267
(2016/01/26)
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- Hydration of alkynes at room temperature catalyzed by gold(I) isocyanide compounds
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An effective method using gold(I) isocyanide complexes as catalysts for the transformation of various alkynes to the corresponding ketones is successfully developed. The hydration process proceeds smoothly at room temperature with quite high yield (up to 99%). The catalytic center is the isocyanide-Au(I)+ cation. Further theoretical research reveals a direct hydration mechanism by H2O, and the rate-determining step has an energy barrier of 23.7 kcal mol?1. These results show a good example to reduce unnecessary steps and achieve milder reaction conditions at the same time for the hydration of alkynes.
- Xu, Yun,Hu, Xingbang,Shao, Jing,Yang, Guoqiang,Wu, Youting,Zhang, Zhibing
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supporting information
p. 532 - 537
(2018/04/16)
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- Facile synthesis of a peptidic Au(i)-metalloamphiphile and its self-assembly into luminescent micelles in water
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We report a short synthetic route for the preparation of a peptidic Au(i)-metalloamphiphile which, in buffered environments of physiological ionic strength, self-assembles into luminescent micellar nanostructures of 14 nm in diameter. This journal is
- Kemper, Benedict,Hristova, Yana R.,Tacke, Sebastian,Stegemann, Linda,Van Bezouwen, Laura S.,Stuart, Marc C. A.,Klingauf, Jürgen,Strassert, Cristian A.,Besenius, Pol
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supporting information
p. 5253 - 5256
(2015/03/30)
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- Facile Gold-Catalyzed Heterocyclization of Terminal Alkynes and Cyanamides Leading to Substituted 2-Amino-1,3-Oxazoles
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Facile gold-catalyzed heterocyclization based upon intermolecular trapping of the generated α-oxo gold carbenes with various cyanamides R2R3NCN (R2/R3 = Alk/Alk, -(CH2)2O(CH2)2-, Ar/Ar, Ar/H) has been developed. In most cases, 2-amino-1,3-oxazoles functionalized at the nitrogen atom as well as at the fifth position of the heterocyclic ring (12 examples) were isolated in good to moderate yields.
- Rassadin, Valentin A.,Boyarskiy, Vadim P.,Kukushkin
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supporting information
p. 3502 - 3505
(2015/07/28)
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- Chiral arrangement of achiral Au nanoparticles by supramolecular assembly of helical nanofiber templates
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Chiral materials composed of organized nanoparticle superstructures have promising applications to photonics and sensing. Reliable customization of the chiroptical properties of these materials remains an important goal; hence, we report a customizable scheme making use of modular gelator components for controlling the helicity and formation of nanofibers over long length scales resulting in hydrogel templates. Controlled growth of gold nanoparticles at spatially arranged locations along the nanofiber is achieved by UV reduction of Au(I) ions on the supramolecular templates. The resulting materials were found to have significant interparticle interactions and well-defined helicity to provide high quality, chiroptically active materials. With this novel approach, the tailored assembly of nanoparticle superstructures with predictable chiroptical properties can be realized in high yield, which we expect to allow rapid advancement of chiral nanomaterials research.
- Jung, Sung Ho,Jeon, Jiwon,Kim, Hyungjun,Jaworski, Justyn,Jung, Jong Hwa
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supporting information
p. 6446 - 6452
(2014/05/20)
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- Gold catalysis: Biarylphosphine ligands as key for the synthesis of dihydroisocoumarins
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Agold-catalyzed phenol synthesis was successfully used in the synthesis of dihydroisocoumarins for the first time.Alarge number of gold(I) complexes were prepared and tested; only complexes based on the biarylphosphine motif were successful. CSIRO 2014.
- Hashmi, A. Stephen K.,Bechem, Benjamin,Loos, Annette,Hamzic, Melissa,Rominger, Frank,Rabaa, Hassan
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p. 481 - 499
(2014/04/03)
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- Leveraging the micellar effect: Gold-catalyzed dehydrative cyclizations in water at room temperature
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The first examples of gold-catalyzed cyclizations of diols and triols to the corresponding hetero- or spirocycles in an aqueous medium are presented. These reactions take place within nanomicelles, where the hydrophobic effect is operating, thereby driving the dehydrations, notwithstanding the surrounding water. By the addition of simple salts such as sodium chloride, reaction times and catalyst loadings can be significantly decreased.
- Minkler, Stefan R. K.,Isley, Nicholas A.,Lippincott, Daniel J.,Krause, Norbert,Lipshutz, Bruce H.
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supporting information
p. 724 - 726
(2014/03/21)
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- Solvent effects in gold-catalysed A3-coupling reactions
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Gold-catalysed A3-reactions proceed efficiently when conducted in 2,2,2-trifluoroethanol as solvent. The rates of these reactions are accelerated considerably when conducted in a microwave reactor.
- Price, Gregory A.,Brisdon, Alan K.,Flower, Kevin R.,Pritchard, Robin G.,Quayle, Peter
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supporting information
p. 151 - 154
(2014/01/06)
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- Reactions of gold(III) complexes with alkenes in aqueous media: Generation of bis-(β-hydroxyalkyl)gold(III) complexes
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Reactions of gold(III) complexes with ethylene and propylene in water provide the first such examples not accompanied by reduction of the gold. HAuC14 and AuCL3(TPPTS) produce organic products (alcohol, aldehyde/ketone, etc.) with gold reduction to the metal. However, [Au(bipy)CL2] Cl in water produces the gold(III) β-hydroxy complexes, [Au(bipy)(CH2CH2OH)2]X (X =Cl, PF6) and [Au(bipy)(CH2CH(OH)CH3]Cl, which are stable in solution. These complexes could not be isolated, but were characterized by NMR and high-resolution mass spectra. [Au(terpy)Cl]CL2 fails to react with ethylene in water, even at elevated temperatures. DFT computations were performed to investigate the reaction mechanism.
- Rezsnyak, Chad E.,Autschbach, Jochen,Atwood, Jim D.,Moncho, Salvador
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p. 1153 - 1165
(2013/07/28)
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- Synthesis of gold(i) fluoroalkyl and fluoroalkenyl-substituted phosphine complexes and factors affecting their crystal packing
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A series of gold(i) phosphine complexes of the type [AuCl{PR 2(Rf)}] (R = Et, i-Pr, Cy; Rf = CFCF 2; R = Ph, Rf = CFCFH, CClCF2, CCCF 3, CF3, i-C3F7, s-C 4F9) have been prepared and most have been structurally characterised. All of the complexes are monomeric in the solid state, and a number of secondary interactions are observed - including short intramolecular Au...F distances, metal-bound Au-Cl...H non-classical hydrogen bonds, fluorous domains and phenyl embraces. Only in the case of [AuCl{PEt 2(CFCF2)}] is an aurophilic interaction with an Au...Au contact less than the sum of the van der Waals radii observed. Even then, the distance, 3.3458(10) A, is longer than that previously observed for the related complex with R = Ph; Rf = CFCF2.
- Barnes, Nicholas A.,Brisdon, Alan K.,William Brown,Cross, Wendy I.,Crossley, Ian R.,Fish, Cheryl,Herbert, Christopher J.,Pritchard, Robin G.,Warren, John E.
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p. 1743 - 1750
(2011/04/15)
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- A complex of gold(I) benzenethiolate with isocyanide: Synthesis and crystal and molecular structures
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2,6-Dimethylphenyl isocyanide forms complexes with gold(I) chloride (complex 4) and gold(I) benzenethiolate (complex 5) but forms no stable complexes with gold alkanethiolates. A reaction of complex 5 with tetramethylthiuram disulfide yields gold(I) dimethyldithiocarbamate. Stable gold(III) derivatives cannot be obtained in such a way. Shortened intermolecular Au...Au contacts in complexes 4 and 5 (X-ray diffraction) suggest the presence of "aurophilic" interactions in them.
- Dyadchenko,Belov,Dyadchenko,Slovokhotov,Banaru,Lemenovskii
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p. 539 - 543
(2011/02/16)
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- Synthesis, crystal and molecular structure of gold(I) thiophenolate with 4′-ferrocenyl[1,1′]biphenylisocyanides
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The syntheses of ferrocenylbiphenylisocyanide gold(I) thiophenolato complexes are described. The preparative route starts from ferrocenylphenylbromide and proceeds in six steps to yield the desired gold(I) complexes, (thiophenolato)gold{(4′-ferrocenyl[1,1′]biphenyl-4-yl)isocya nide} (11) and (thiophenolato)gold{(4′-ferrocenyl-3,5-dimethyl[1,1′]bipheny l-4-yl)isocyanide} (12) in good yields. The synthetic pathways were developed as a first step toward realizing the goal of preparing metallomesogens based on ferrocenyl-polyphenylenes coordinated to gold(I) thiophenolates, in which long chain alkoxy groups are substituted para to sulfur on the phenyl ring. The crystal structures of (chloro)gold{(4′-ferrocenyl[1,1′]biphenyl-4-yl)is ocyanide} (9) and 12 are reported. Complex 9 crystallizes in the space group P21/c and 12 crystallizes in P21/n. Complexes 9 and 12 show short intermolecular Au-Au contacts of 3.3765(7) ? and 3.3334(3) ?, respectively.
- Dyadchenko,Belov,Lemenovskii,Antipin,Lyssenko,Bruce,Bruce
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p. 304 - 309
(2010/03/30)
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- Group 11 complexes of the P,Te-centered ligand [TePiPr 2NPiPr2]": synthesis, structures, and insertion reactions of the copper(l) complex with chalcogens
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The lithium reagent [LiTePiPr2NPiPr 2] undergoes metathetical reactions with group 11 chlorides to give the complexes {M(TePiPr2NPiPr 2)}3 (6: M = Cu; 7: M
- Ritch, Jamie S.,Chivers, Tristram
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p. 3857 - 3865
(2009/08/15)
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- Naphtholactame as a ligand
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Deprotonation of the fluorophore N-Benz[cd]indol-2(1H)-on (= naphtholactame) with NaN(SiMe3)2 yields the naphtholactamate 1, which is subsequently reacted with the chloro complexes [Ph3PAuCl] and [(Ph3P)2PtCl2]. The mono- and disubstitution products [Ph3PAu(C11H6NO)] (2), [(Ph3P)2PtCl(C11H6NO)] (3) and [(Ph3P)2Pt(C11H6NO)2] (4) with one (2, 3) or two (4) metal-N-bonds respectively, were isolated. Substitution of chloride in the phosphanes Ph3-nPCln with 1 leads to the naphtholactamato-N-phosphane derivatives Ph3-nP(C11H6NO)n (n = 3 (5), 2 (6), 1 (7)). 7, which is particularly sensitive towards air oxygen, is readily oxidized to give the corresponding phosphane oxide Ph2P(O)(C11H6NO) (8). The ligating properties of 5 and 7 have been examined. In a two-step reaction HAuCl4, C4H8S (= THT) and 7 yield the phosphane complex [{Ph2(C11H6NO)P} AuCl] (9). Photolytic activation of W(CO)6 in THF and subsequent addition of 5 or 7 surprisingly leads to the tetracarbonyl complexes [(CO)4W{P(C11H6NO)2(C 11H6NO)}] (10) and [(CO)4W {PPh2(C11H6N0)}] (11), respectively. Both exhibit a bidentate P,O-bound naphtholactamatophosphane ligand. The compounds have been characterized by their IR-, NMR- and Mass spectra, compound 11 additionally by a single crystal structure analysis. Theoretical studies on PM3-level for 5, including a structure optimization and as well as an NBO analysis, have been carried out.
- Limmert, Michael,Lorenz, Ingo-Peter,Neubauer, Juergen,Schulz, Axel,Piotrowski, Holger
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p. 223 - 231
(2008/10/08)
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