39929-21-0Relevant articles and documents
Tris(mercaptoimidazolyl)borate complexes of the coinage metals: Syntheses and molecular structures of the first gold compounds and related copper and silver derivatives
Patel, Denish V.,Mihalcik, David J.,Kreisel, Kevin A.,Yap, Glenn P. A.,Zakharov, Lev N.,Kassel, W. Scott,Rheingold, Arnold L.,Rabinovich, Daniel
, p. 2410 - 2416 (2005)
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
Hierarchy of Supramolecular Arrangements and Building Blocks: Inverted Paradigm of Crystal Engineering in the Unprecedented Metal Coordination of Methylene Blue
Canossa, Stefano,Bacchi, Alessia,Graiff, Claudia,Pelagatti, Paolo,Predieri, Giovanni,Ienco, Andrea,Manca, Gabriele,Mealli, Carlo
, p. 3512 - 3516 (2017)
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.
Bright Luminescence in Three Phases—A Combined Synthetic, Spectroscopic and Theoretical Approach
Dahlen, Milena,Gamer, Michael T.,Hollesen, Eike H.,Kappes, Manfred M.,Kehry, Max,Klopper, Wim,Lebedkin, Sergei,Roesky, Peter W.,Schooss, Detlef
, p. 23365 - 23372 (2021)
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.
Preparation of an organometallic molecular square by self-assembly of phosphorus-containing building blocks
Malberg, Jennifer,Bodensteiner, Michael,Paul, Daniel,Wiegand, Thomas,Eckert, Hellmut,Wolf, Robert
, p. 2771 - 2775 (2014)
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.
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)
Whittall, Ian R.,Humphrey, Mark G.,Samoc, Marek,Luther-Davies, Barry,Hockless, David C.R.
, p. 189 - 196 (1997)
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.
Bi- And trinuclear coinage metal complexes of a PNNP ligand featuring metallophilic interactions and an unusual charge separation
Dahlen, Milena,Kappes, Manfred M.,Kehry, Max,Klopper, Wim,Lebedkin, Sergei,Roesky, Peter W.
supporting information, p. 13412 - 13420 (2021/10/12)
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.
Metal-to-Metal Distance Modulated Au(I)/Ru(II) Cyclophanyl Complexes: Cooperative Effects in Photoredox Catalysis
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
supporting information, p. 15187 - 15200 (2021/11/01)
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
A Macrocyclic Gold(I)–Biphenylene Complex: Triangular Molecular Structure with Twisted Au2(diphosphine) Corners and Reductive Elimination of [6]Cycloparaphenylene
Abe, Ryota,Ide, Tomohito,Osakada, Kohtaro,Tsuchido, Yoshitaka
supporting information, p. 22928 - 22932 (2020/09/02)
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
Gold(I)-Catalysed Hydroarylation of Lactam-Derived Enynes as an Entry to Tetrahydrobenzo[g]quinolines
Nejrotti, Stefano,Ghinato, Simone,Gini, Elena C.,Scarpi, Dina,Occhiato, Ernesto G.,Maranzana, Andrea,Prandi, Cristina
supporting information, p. 646 - 653 (2019/12/27)
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.
Selective Synthesis of ortho-Substituted Diarylsulfones by Using NHC-Au Catalysts under Mild Conditions
Zhu, Haibo,Shen, Yajing,Wen, Daheng,Le, Zhang-Gao,Tu, Tao
supporting information, p. 974 - 979 (2019/02/14)
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.
