共查询到20条相似文献,搜索用时 15 毫秒
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Ganesan Prabusankar Dr. Christian Gemel Dr. Manuela Winter Rüdiger W. Seidel Roland A. Fischer Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(20):6041-6047
Heavy‐metal complexes of lead and mercury stabilized by Group 13 ligands were derived from the oxidative addition of Ga(ddp) (ddp=HC(CMeNC6H3‐2,6‐iPr2)2, 2‐diisopropylphenylamino‐4‐diisopropyl phenylimino‐2‐pentene) with corresponding metal precursors. The reaction of Me3PbCl and Ga(ddp) afforded compound [{(ddp)Ga(Cl)}PbMe3] ( 1 ) composed of Ga? PbIV bonds. In addition, the monomeric plumbylene‐type compound [{(ddp)Ga(OSO2CF3)}2Pb(thf)] ( 2 a ) with an unsupported Ga‐PbII‐Ga linkage was obtained by the reaction of [Pb(OSO2CF3)3] with Ga(ddp) (2 equiv). Compound 2 a falls under the rare example of a discrete plumbylene‐type compound supported by a nonclassical ligand. Interesting structural changes were observed when [Pb(OSO2CF3)3] ? 2 H2O was treated with Ga(ddp) in a 1:2 ratio to yield [{(ddp)Ga(μ‐OSO2CF3)}2(OH2)Pb] ( 2 b ) at below ?10 °C. Compound 2 b consists of a bent Ga‐Pb‐Ga backbone with a bridging triflate group between the Ga? Pb bond and a weakly interacting water molecule at the gallium center. Similarly, the reaction of mercury thiolate Hg(SC6F5) with Ga(ddp) (2 equiv) produced the bimetallic homoleptic compounds anti‐[{(ddp)Ga(SC6F5)}2Hg] ( 3 a ) and gauche‐[{(ddp)Ga(SC6F5)}2Hg] ( 3 b ), respectively, with a linear Ga‐Hg‐Ga linkage. Compounds 1 – 3 were structurally characterized and these are the first examples of compounds comprised of Ga? PbII, Ga? PbIV, and Ga? Hg bonds. 相似文献
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Intramolecularly Stabilised Group 10 Metal Stannyl and Stannylene Complexes: Multi‐pathway Synthesis and Observation of Platinum‐to‐Tin Alkyl Transfer 下载免费PDF全文
Cornelis A. Boon Dr. Yves Cabon Dr. Jeroen J. M. de Pater Dr. Martin Lutz Prof. Dr. Robertus J. M. Klein Gebbink Prof. Dr. Berth‐Jan Deelman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1765-1779
Reaction of [PdClMe(P^N)2] with SnCl2 followed by Cl‐abstraction leads to apparent Pd?C bond activation, resulting in methylstannylene species trans‐[PdCl{(P^N)2SnClMe}][BF4] (P^N=diaryl phosphino‐N‐heterocycle). In contrast, reaction of Pt analogues with SnCl2 leads to Pt?Cl bond activation, resulting in methylplatinum species trans‐[PtMe{(P^N)2SnCl2}][BF4]. Over time, they isomerise to methylstannylene species, indicating that both kinetic and thermodynamic products can be isolated for Pt, whereas for Pd only methylstannylene complexes are isolated. Oxidative addition of RSnCl3 (R=Me, Bu, Ph) to M0 precursors (M=Pd or Pt) in the presence of P^N ligands results in diphosphinostannylene pincer complexes trans‐[MCl{(P^N)2SnCl(R)}][SnCl4R], which are structurally similar to the products from SnCl2 insertion. This showed that addition of RSnCl3 to M0 results in formal Sn?Cl bond oxidative addition. A probable pathway of activation of the tin reagents and formation of different products is proposed and the relevancy of the findings for Pd and Pt catalysed processes that use SnCl2 as a co‐catalyst is discussed. 相似文献
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Susanne Büschel Dipl.‐Chem. Ann‐Katrin Jungton Dipl.‐Chem. Thomas Bannenberg Dr. Sören Randoll Dr. Cristian G. Hrib Dr. Peter G. Jones Prof. Dr. Matthias Tamm Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(9):2176-2184
Twice as reactive : The coordination chemistry of phosphane‐functionalized Zr and Hf cycloheptatrienyl–cyclopentadienyl complexes gives rise to unusual secondary interactions associated with the presence of Lewis acidic 16‐electron sandwich moieties. These structures can develop weak dative bonds as exemplified by the noncovalent Pd→Zr interaction in the heterobimetallic {Zr2Pd} complex (see picture).
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Synthesis of Triangular Tripalladium Cations as Noble‐Metal Analogues of the Cyclopropenyl Cation 下载免费PDF全文
Dr. Sébastien Blanchard Prof. Louis Fensterbank Geoffrey Gontard Dr. Emmanuel Lacôte Dr. Giovanni Maestri Prof. Max Malacria 《Angewandte Chemie (International ed. in English)》2014,53(7):1987-1991
The first C3‐symmetric 44‐core‐valence‐electron triangular palladium clusters, [{(SAr′)(PAr3)Pd}3]+, have been synthesized by activation of the C? S bond of isothioureas. Owing to delocalized metal–metal bonding, these stable complexes are the first noble‐metal analogues of the π‐aromatic cyclopropenyl cation [C3H3]+, with their all‐metal aromaticity involving d‐type atomic orbitals. 相似文献
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Dr. Mikhail V. Butovskii Dr. Benjamin Oelkers Dr. Tobias Bauer Dr. Jacinta M. Bakker Dr. Viktor Bezugly Dr. Frank R. Wagner Prof. Dr. Rhett Kempe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(10):2804-2811
Bismetallocenes [Cp2LuReCp2] and [Cp*2LaReCp2] (Cp=cyclopentadienyl; Cp*=pentamethylcyclopentadienyl) were prepared using different synthetic strategies. Salt metathesis—performed in aromatic hydrocarbons to avoid degradation pathways caused by THF—were identified as an attractive alternative to alkane elimination. Although alkane elimination is more attractive in the sense of its less elaborate workup, the rate of the reaction shows a strong dependence on the ionic radius of Ln3+ (Ln=lanthanide) within a given ligand set. Steric hindrance can cause a dramatic decrease in the reaction rate of alkane elimination. In this case, salt metathesis should be considered the better alternative. Covalent bonding interactions between the Ln and transition‐metal (TM) cations has been quantified on the basis of the delocalization index. Its magnitude lies within the range characteristic for bonds between transition metals. Secondary interactions were identified between carbon atoms of the Cp ligand of the transition metal and the Ln cation. Model calculations clearly indicated that the size of these interactions depends on the capability of the TM atom to act as an electron donor (i.e., a Lewis base). The consequences can even be derived from structural details. The observed clear dependency of the Lu?Ru and interfragment Lu?C bonding on the THF coordination of the Lu atom points to a tunable Lewis acidity at the Ln site, which provides a method of significantly influencing the structure and the interfragment bonding. 相似文献
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Keisuke Umakoshi Prof. Dr. Keizo Saito Yasuhiro Arikawa Dr. Masayoshi Onishi Prof. Shoji Ishizaka Dr. Noboru Kitamura Prof. Dr. Yoshihide Nakao Dr. Shigeyoshi Sakaki Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(17):4238-4242
Swap the coins! The Pt2Au2, Pt2Au2Cu2, and Pt2Au2Ag2 complexes of 3,5‐dimethylpyrazolate exhibit yellow‐green, orange, and sky‐blue luminescence, respectively (see figure). The emission energies of Pt2Au2M2 complexes can be controlled by the change of the third coinage metal ions M. The Pt2Au2M2 complexes take the cis configuration with respect to the Au2M2 plane.
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Dr. Chelladurai Ganesamoorthy Dieter Bläser Dr. Christoph Wölper Prof. Dr. Stephan Schulz 《Angewandte Chemie (International ed. in English)》2014,53(43):11587-11591
Monovalent RAl (R=HC[C(Me)N(2,6‐iPr2C6H3)]2) reacts with E2Et4 (E=Sb, Bi) with insertion into the weak E? E bond and subsequent formation of RAl(EEt2)2 (E=Sb 1 ; Bi 2 ). The analogous reactions of RGa with E2Et4 yield a temperature‐dependent equilibrium between RGa(EEt2)2 (E=Sb 3 ; Bi 4 ) and the starting reagents. RIn does not interact with Sb2Et4 under various reaction conditions, but formation of RIn(BiEt2)2 ( 5 ) was observed in the reaction with Bi2Et4 at low temperature. 相似文献
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Philipp Bissinger Prof. Dr. Holger Braunschweig Dr. Alexander Damme Dr. Rian D. Dewhurst Dr. Katharina Kraft Thomas Kramer Dr. Krzysztof Radacki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13402-13407
The synthesis of base‐stabilized boryl and borylene complexes is reported. An N‐heterocyclic carbene (NHC)‐stabilized iron–dihydroboryl complex was prepared by two different routes including methane liberation and salt elimination. A range of base‐stabilized iron–dichloroboryl complexes was prepared by addition of Lewis bases to boryl complexes. Base‐stabilized, cationic monochloroborylene complexes were synthesized from these boryl complexes by halide abstraction by using weakly coordinating anions. 相似文献
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Isolation of a Neutral Boron‐Containing Radical Stabilized by a Cyclic (Alkyl)(Amino)Carbene 下载免费PDF全文
Dr. Philipp Bissinger Prof. Dr. Holger Braunschweig Dr. Alexander Damme Dr. Ivo Krummenacher Dr. Ashwini K. Phukan Dr. Krzysztof Radacki Shun Sugawara 《Angewandte Chemie (International ed. in English)》2014,53(28):7360-7363
Utilizing a cyclic (alkyl)(amino)carbene (CAAC) as a ligand, neutral CAAC‐stabilized radicals containing a boryl functionality could be prepared by reduction of the corresponding haloborane adducts. The radical species with a duryl substituent was fully characterized by single‐crystal X‐ray structural analysis, EPR spectroscopy, and DFT calculations. Compared to known neutral boryl radicals, the isolated radical species showed larger spin density on the boron atom. Furthermore, the compound that was isolated is extraordinarily stable to high temperatures under inert conditions, both in solution and in the solid state. Electrochemical investigations of the radical suggest the possibility to generate a stable formal boryl anion species. 相似文献
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Jia‐Qi Wang Chaoxian Chi Han‐Shi Hu Xiang Li Mingbiao Luo Jun Li Mingfei Zhou 《Angewandte Chemie (International ed. in English)》2020,59(6):2344-2348
Heteronuclear Group 3 metal/iron carbonyl anion complexes ScFe(CO)3?, YFe(CO)3?, and LaFe(CO)3? are prepared in the gas phase and studied by mass‐selective infrared (IR) photodissociation spectroscopy as well as quantum‐chemical calculations. All three anion complexes are characterized to have a metal–metal‐bonded C3v equilibrium geometry with all three carbonyl ligands bonded to the iron center and a closed‐shell singlet electronic ground state. Bonding analyses reveal that there are multiple bonding interactions between the bare group‐3 elements and the Fe(CO)3? fragment. Besides one covalent electron‐sharing metal–metal σ bond and two dative π bonds from Fe to the Group 3 metal, there is additional multicenter covalent bonding with the Group 3 atom bonded to Fe and the carbon atoms. 相似文献
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Crystallographic Evidence for Direct Metal–Metal Bonding in a Stable Open‐Shell La2@Ih‐C80 Derivative 下载免费PDF全文
Lipiao Bao Dr. Muqing Chen Changwang Pan Takahisa Yamaguchi Prof. Tatsuhisa Kato Prof. Marilyn M. Olmstead Prof. Alan L. Balch Prof. Takeshi Akasaka Prof. Xing Lu 《Angewandte Chemie (International ed. in English)》2016,55(13):4242-4246
Endohedral metallofullerenes (EMFs) have novel structures and properties that are closely associated with the internal metallic species. Benzyl radical additions have been previously shown to form closed‐shell adducts by attaching an odd number of addends to open‐shell EMFs (such as Sc3C2@Ih‐C80) whereas an even number of groups are added to closed‐shell EMFs (for example Sc3N@Ih‐C80). Herein we report that benzyl radical addition to the closed‐shell La2@Ih‐C80 forms a stable, open‐shell monoadduct instead of the anticipated closed‐shell bisadduct. Single‐crystal X‐ray diffraction results show the formation of a stable radical species. In this species, the La?La distance is comparable to the theoretical value of a La?La covalent bond and is shorter than reported values for other La2@Ih‐C80 derivatives, providing unambiguous evidence for the formation of direct La?La bond. 相似文献
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Unprecedented Efficient Structure Controlled Phosphorescence of Silver(I) Clusters Stabilized by Carba‐closo‐dodecaboranylethynyl Ligands 下载免费PDF全文
Michael Hailmann Natalia Wolf Rebecca Renner Thomas C. Schäfer Benjamin Hupp Dr. Andreas Steffen Prof. Dr. Maik Finze 《Angewandte Chemie (International ed. in English)》2016,55(35):10507-10511
{Ag2(12‐C≡C‐closo‐1‐CB11H11)}n and selected pyridine ligands have been used for the synthesis of photostable AgI clusters that, with one exception, exhibit for AgI compounds unusual room‐temperature phosphorescence. Extraordinarily intense phosphorescence was observed for a distorted pentagonal bipyramidal AgI7 cluster that shows an unprecedented quantum yield of Φ=0.76 for AgI clusters. The luminescence properties correlate with the structures of the central AgIn motifs as shown by comparison of the emission properties of the clusters with different numbers of AgI ions, different charges, and electronically different pyridine ligands. 相似文献