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1.
Martin Piesch Christian Graßl Manfred Scheer 《Angewandte Chemie (International ed. in English)》2020,59(18):7154-7160
The redox chemistry of [(Cp′′′Co)2(μ,η2:η2‐E2)2] (E=P ( 1 ), As ( 2 ); Cp′′′=1,2,4‐tri(tert‐butyl)cyclopentadienyl) was investigated. Both compounds can be oxidized and reduced twice. That way, the monocations [(Cp′′′Co)2(μ,η4:η4‐E4)][X] (E=P, X=BF4 ( 3 a ), [FAl] ( 3 b ); E=As, X=BF4 ( 4 a ), [FAl] ( 4 b )), the dications [(Cp′′′Co)2(μ,η4:η4‐E4)][TEF]2 (E=P ( 5 ), As ( 6 )), and the monoanions [K(18‐c‐6)(dme)2][(Cp′′′Co)2(μ,η4:η4‐E4)] (E=P ( 7 ), As ( 8 )) were isolated. Further reduction of 7 leads to the dianionic complex [K(18‐c‐6)(dme)2][K(18‐c‐6)][(Cp′′′Co)2(μ,η3:η3‐P4)] ( 9 ), in which the cyclo‐P4 ligand has rearranged to a chain‐like P4 ligand. Further reduction of 8 can be achieved with an excess of potassium under the formation of [K(dme)4][(Cp′′′Co)2(μ,η3:η3‐As3)] ( 10 ) and the elimination of an As1 unit. Compound 10 represents the first example of an allylic As3 ligand incorporated into a triple‐decker complex. 相似文献
2.
Martin Piesch Stephan Reichl Michael Seidl Gbor Balzs Manfred Scheer 《Angewandte Chemie (International ed. in English)》2019,58(46):16563-16568
The reaction of [Cp′′′Co(η4‐P4)] ( 1 ) (Cp′′′=1,2,4‐tBu3C5H2) with MeNHC (MeNHC=1,3,4,5‐tetramethylimidazol‐2‐ylidene) leads through NHC‐induced phosphorus cation abstraction to the ring contraction product [(MeNHC)2P][Cp′′′Co(η3‐P3)] ( 2 ), which represents the first example of an anionic CoP3 complex. Such NHC‐induced ring contraction reactions are also applicable for triple‐decker sandwich complexes. The complexes [(Cp*Mo)2(μ,η6:6‐E6)] ( 3 a , 3 b ) (Cp*=C5Me5; E=P, As) can be transformed to the complexes [(MeNHC)2E][(Cp*M)2(μ,η3:3‐E3)(μ,η2:2‐E2)] ( 4 a , 4 b ), with 4 b representing the first structurally characterized example of an NHC‐substituted AsI cation. Further, the reaction of the vanadium complex [(Cp*V)2(μ,η6:6‐P6)] ( 5 ) with MeNHC results in the formation of the unprecedented complexes [(MeNHC)2P][(Cp*V)2(μ,η6:6‐P6)] ( 6 ), [(MeNHC)2P][(Cp*V)2(μ,η5:5‐P5)] ( 7 ) and [(Cp*V)2(μ,η3:3‐P3)(μ,η1:1‐P{MeNHC})] ( 8 ). 相似文献
3.
《Angewandte Chemie (International ed. in English)》2017,56(32):9592-9596
Reactions between the 1,3‐diphosphete complex [Cp′′′Co(η4‐P2C2tBu2)] ( 1 ) and Ag[Al{OC(CF3)3}4] (Ag[pftb]) were carried out under different conditions. In CH2Cl2, the unprecedented 1,2‐diphosphete isomerization product [Ag2{Cp′′′Co(μ,η4:η1:η1‐1,2‐P2C2tBu2)}2{Cp′′′Co(μ,η4:η1‐1,2‐P2C2tBu2)}2]⋅2[pftb] ( 2 ) could be isolated. In diffusion experiments of 1 in n‐hexane with Ag[pftb] in CH2Cl2, the triphosphacobaltocenium complex [Cp′′′Co(η5‐P3C2tBu2)][pftb] ( 4 ) and the phosphirenylium complex [Cp′′′Co(η3‐PC2tBu2)][pftb] ( 5 ) were obtained, showing a ring expansion and a ring contraction, respectively, under mild conditions. Moreover, addition of pyridine to the Ag complex 2 led to the new 1,2‐diphosphete complex [Cp′′′Co(η4‐1,2‐P2C2tBu2)] ( 3 ). Compound 3 is also formed by thermolysis of 1 , making it a promising method for this type of isomerization. 1,2‐Diphosphete complexes like 3 are thermodynamically more stable but also synthetically more elusive than their 1,3‐isomer counterparts. 相似文献
4.
Dr. Martin Piesch Stephan Reichl Christoph Riesinger Dr. Michael Seidl Dr. Gabor Balazs Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(35):9129-9140
The redox chemistry of the heterobimetallic triple-decker complexes [(Cp*Fe)(Cp′′′Co)(μ,η5:η4-E5)] (E=P ( 1 ), As ( 2 ), Cp*=1,2,3,4,5-pentamethyl-cyclopentadienyl, Cp′′′=1,2,4-tri-tertbutyl-cyclopentadienyl) and [(Cp′′′Co)(Cp′′′Ni)(μ,η3:η3-E3)] (E=P ( 10 ), As ( 11 )) was investigated. Compound 1 and 2 could be oxidized to the monocations 3 and 4 and further to the dications 5 and 6 , while the initially folded cyclo-E5 ligand planarizes upon oxidation. The reduction leads to an opposite change in the geometry of the middle deck, which is now folded stronger into the direction of the other metal fragment (formation of monoanions 7 and 8 ). For the arsenic compound 8 , a different behavior is found since a fragmentation into an As6 ( 9 ) and As3 ligand complex occurs. The Co and Ni triple-decker complexes 10 and 11 can be oxidized initially to the heterometallic monocations 12 and 13 , which are not stable in solution and convert selectively into the homometallic nickel complexes 14 and 15 and the cobalt complexes 16 and 17 . This behavior was further proven by the oxidation of [(Cp′′′Co)(Cp′′Ni)(μ,η3:η2-P3)] ( 19 , Cp′′=1,3-di-tertbutyl-cyclopentadienyl) comprising two different Cp ligands. The transfer of {CpRM} fragments can be suppressed when a {W(CO)5} unit is coordinated to the P3 ligand ( 20 ) prior to the oxidation and the mixed cobalt and nickel cation 21 can be isolated. The reduction of 10 and 11 yields the heterometallic monoanions 22 and 23 , where no transfer of the {CpRM} fragments is observed. 相似文献
5.
Martin Piesch Dr. Fabian Dielmann Stephan Reichl Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(7):1518-1524
A systematic study on the reactivity of the triple-decker complex [(Cp’’’Co)2(μ,η4:η4-C7H8)] ( A ) (Cp’’’=1,2,4-tritertbutyl-cyclopentadienyl) towards sandwich complexes containing cyclo-P3, cyclo-P4, and cyclo-P5 ligands under mild conditions is presented. The heterobimetallic triple-decker sandwich complexes [(Cp*Fe)(Cp’’’Co)(μ,η5:η4-P5)] ( 1 ) and [(Cp’’’Co)(Cp’’’Ni)(μ,η3:η3-P3)] ( 3 ) (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) were synthesized and fully characterized. In solution, these complexes exhibit a unique fluxional behavior, which was investigated by variable temperature NMR spectroscopy. The dynamic processes can be blocked by coordination to {W(CO)5} fragments, leading to the complexes [(Cp*Fe)(Cp’’’Co)(μ3,η5:η4:η1-P5){W(CO)5}] ( 2 a ), [(Cp*Fe)(Cp’’’Co)(μ4,η5:η4:η1:η1-P5){(W(CO)5)2}] ( 2 b ), and [(Cp’’’Co)(Cp’’’Ni)(μ3,η3:η2:η1-P3){W(CO)5}] ( 4 ), respectively. The thermolysis of 3 leads to the tetrahedrane complex [(Cp’’’Ni)2(μ,η2:η2-P2)] ( 5 ). All compounds were fully characterized using single-crystal X-ray structure analysis, NMR spectroscopy, mass spectrometry, and elemental analysis. 相似文献
6.
Martin Piesch Stephan Reichl Michael Seidl Gbor Balzs Manfred Scheer 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(46):16716-16721
Die Reaktion von [Cp′′′Co(η4‐P4)] ( 1 ) (Cp′′′=1,2,4‐tBu3C5H2) mit MeNHC (MeNHC=1,3,4,5‐tetramethylimidazol‐2‐ylidene) führt über eine NHC‐induzierte Phosphorkationen‐Abstraktion zum Ringkontraktionsprodukt [(MeNHC)2P][Cp′′′Co(η3‐P3)] ( 2 ), welches das erste Beispiel eines anionischen CoP3‐Komplexes repräsentiert. Solche von NHCs induzierten Ringkontraktionsreaktionen lassen sich ebenfalls auf Tripeldecker‐Sandwich‐Komplexe anwenden. So werden die Komplexe [(Cp*Mo)2(μ,η6:6‐E6)] ( 3 a , 3 b ) (Cp*=C5Me5; E=P, As) zu den Komplexen [(MeNHC)2E][(Cp*M)2(μ,η3:3‐E3)(μ,η2:2‐E2)] ( 4 a , 4 b ) transformiert, wobei 4 b das erste strukturell charakterisierte Beispiel eines NHC‐substituierten AsI‐Kations darstellt. Darüber hinaus führt die Reaktion des Vanadium‐Komplexes [(Cp*V)2(μ,η6:6‐P6)] ( 5 ) mit MeNHC zur Bildung der neuartigen Komplexe [(MeNHC)2P][(Cp*V)2(μ,η6:6‐P6)] ( 6 ), [(MeNHC)2P][(Cp*V)2(μ,η5:5‐P5)] ( 7 ) bzw. [(Cp*V)2(μ,η3:3‐P3)(μ,η1:1‐P{MeNHC})] ( 8 ). 相似文献
7.
Dr. Christoph Schwarzmaier Dr. Sebastian Heinl Dr. Gábor Balázs Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2015,54(44):13116-13121
The coordination properties of new types of bidentate phosphane and arsane ligands with a narrow bite angle are reported. The reactions of [{Cp′′′Fe(CO)2}2(μ,η1:1‐P4)] ( 1 a ) with the copper salt [Cu(CH3CN)4][BF4] leads, depending on the stoichiometry, to the formation of the spiro compound [{{Cp′′′Fe(CO)2}2(μ3,η1:1:1:1‐P4)}2Cu]+[BF4]? ( 2 ) or the monoadduct [{Cp′′′Fe(CO)2}2(μ3,η1:1:2‐P4){Cu(MeCN)}]+[BF4]? ( 3 ). Similarly, the arsane ligand [{Cp′′′Fe(CO)2}2(μ,η1:1‐As4)] ( 1 b ) reacts with [Cu(CH3CN)4][BF4] to give [{{Cp′′′Fe(CO)2}2(μ3,η1:1:1:1‐As4)}2Cu]+[BF4]? ( 5 ). Protonation of 1 a occurs at the “wing tip” phosphorus atoms, which is in line with the results of DFT calculations. The compounds are characterized by spectroscopic methods (heteronuclear NMR spectroscopy and IR spectrometry) and by single‐crystal X‐ray diffraction studies. 相似文献
8.
M. Sc. Julian Müller Dr. Sebastian Heinl Dr. Christoph Schwarzmaier Dr. Gábor Balázs M. Sc. Martin Keilwerth Prof. Dr. Karsten Meyer Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2017,56(25):7312-7317
The versatile coordination behavior of the P4 butterfly complex [{Cp′′′Fe(CO)2}2(μ,η1:1-P4)] ( 1 , Cp′′′=η5-C5H2tBu3) towards different iron(II) compounds is presented. The reaction of 1 with [FeBr2⋅dme] (dme=dimethoxyethane) leads to the chelate complex [{Cp′′′Fe(CO)2}2(μ3,η1:1:2-P4){FeBr2}] ( 2 ), whereas, in the reaction with [Fe(CH3CN)6][PF6]2, an unprecedented rearrangement of the P4 butterfly structural motif leads to the cyclo-P4 moiety in {(Cp′′′Fe(CO)2)2(μ3,η1:1:4-P4)}2Fe][PF6]2 ( 3 ). Complex 3 represents the first fully characterized “carbon-free” sandwich complex containing cyclo-P4R2 ligands in a homoleptic-like iron–phosphorus-containing molecule. Alternatively, 2 can be transformed into 3 by halogen abstraction and subsequent coordination of 1 . The additional isolated side products, [{Cp′′′Fe(CO)2}2(μ3,η1:1:2-P4){Cp′′′Fe(CO)}][PF6] ( 4 ) and [{Cp′′′Fe(CO)2}2(μ3,η1:1:4-P4){Cp′′′Fe}][PF6] ( 5 ), give insight into the stepwise activation of the P4 butterfly moiety in 1 . 相似文献
9.
Dr. Christoph Schwarzmaier Dr. Michael Bodensteiner Dr. Alexey Y. Timoshkin Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2014,53(1):290-293
The reaction of a P4 butterfly complex with yellow arsenic yields the largest mixed PnAsm ligand complexes synthesized to date. [{Cp′′′Fe(CO)2}2(μ,η1:1‐P4)] reacts with As4 to yield [{Cp′′′Fe}2(μ,η4:4‐PnAs4‐n)] and [Cp′′′Fe(η5‐PnAs5‐n)]. Mass spectrometry together with NMR spectroscopy and X‐ray crystallography give clear evidence about the arrangement of the E positions within the cyclo‐E5 and E4 moieties of the products. Moreover, the results of DFT calculations agree well with the experimental determined outcomes. By coordinating the E4 complex [{Cp′′′Fe}2(μ,η4:4‐PnAs4‐n)] with CuCl, a rearrangement of the E positions occurs in favor with a preferred phosphorus coordination towards copper atoms in the resulting 1D polymeric chain. 相似文献
10.
Helena Brake Eugenia Peresypkina Alexander V. Virovets Martin Piesch Werner Kremer Lisa Zimmermann Christian Klimas Manfred Scheer 《Angewandte Chemie (International ed. in English)》2020,59(37):16241-16246
In a high‐yield one‐pot synthesis, the reactions of [Cp*M(η5‐P5)] (M=Fe ( 1 ), Ru ( 2 )) with I2 resulted in the selective formation of [Cp*MP6I6]+ salts ( 3 , 4 ). The products comprise unprecedented all‐cis tripodal triphosphino‐cyclotriphosphine ligands. The iodination of [Cp*Fe(η5‐As5)] ( 6 ) gave, in addition to [Fe(CH3CN)6]2+ salts of the rare [As6I8]2? (in 7 ) and [As4I14]2? (in 8 ) anions, the first di‐cationic Fe‐As triple decker complex [(Cp*Fe)2(μ,η5:5‐As5)][As6I8] ( 9 ). In contrast, the iodination of [Cp*Ru(η5‐As5)] ( 10 ) did not result in the full cleavage of the M?As bonds. Instead, a number of dinuclear complexes were obtained: [(Cp*Ru)2(μ,η5:5‐As5)][As6I8]0.5 ( 11 ) represents the first Ru‐As5 triple decker complex, thus completing the series of monocationic complexes [(CpRM)2(μ,η5:5‐E5)]+ (M=Fe, Ru; E=P, As). [(Cp*Ru)2As8I6] ( 12 ) crystallizes as a racemic mixture of both enantiomers, while [(Cp*Ru)2As4I4] ( 13 ) crystallizes as a symmetric and an asymmetric isomer and features a unique tetramer of {AsI} arsinidene units as a middle deck. 相似文献
11.
Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)2(μ,η6:η6‐P6)] Towards the “Naked” Cations Cu+, Ag+, and Tl+ 下载免费PDF全文
Martin Fleischmann Fabian Dielmann Laurence J. Gregoriades Eugenia V. Peresypkina Alexander V. Virovets Sebastian Huber Alexey Y. Timoshkin Gbor Balzs Manfred Scheer 《Angewandte Chemie (International ed. in English)》2015,54(44):13110-13115
Although the cyclo‐P6 complex [(Cp*Mo)2(μ,η6:η6‐P6)] ( 1 ) was reported 30 years ago, little is known about its chemistry. Herein, we report a high‐yielding synthesis of 1 , the complex 2 , which contains an unprecedented cyclo‐P10 ligand, and the reactivity of 1 towards the “naked” cations Cu+, Ag+, and Tl+. Besides the formation of the single oxidation products 3 a,b which have a bisallylic distorted cyclo‐P6 middle deck, the [M( 1 )2]+ complexes are described which show distorted square‐planar (M=Cu( 4 a ), Ag( 4 b )) or distorted tetrahedral coordinated (M=Cu( 5 )) M+ cations. The choice of solvent enabled control over the reaction outcome for Cu+, as proved by powder XRD and supported by DFT calculations. The reaction with Tl+ affords a layered two‐dimensional coordination network in the solid state. 相似文献
12.
Veronika Heinl Dr. Monika Schmidt Dr. Maria Eckhardt Dr. Miriam Eberl Dr. Andreas E. Seitz Dr. Gábor Balázs Dr. Michael Seidl Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(45):11649-11655
The use of [Cp′′2Zr(η1:1-E4)] (E=P ( 1 a ), As ( 1 b ), Cp′′=1,3-di-tert-butyl-cyclopentadienyl) as phosphorus or arsenic source, respectively, gives access to novel stable polypnictogen transition metal complexes at ambient temperatures. The reaction of 1 a/1 b with [CpRNiBr]2 (CpR=CpBn (1,2,3,4,5-pentabenzyl-cyclopentadienyl), Cp′′′ (1,2,4-tri-tert-butyl-cyclopentadienyl)) was studied, to yield novel complexes depending on steric effects and stoichiometric ratios. Besides the transfer of the complete En unit, a degradation as well as aggregation can be observed. Thus, the prismane derivatives [(Cp′′′Ni)2(μ,η3:3-E4)] ( 2 a (E=P); 2 b (E=As)) or the arsenic containing cubane [(Cp′′′Ni)3(μ3-As)(As4)] ( 5 ) are formed. Furthermore, the bromine bridged cubanes of the type [(CpRNi)3{Ni(μ-Br)}(μ3-E)4]2 (CpR=Cp′′′: 6 a (E=P), 6 b (E=As), CpR=CpBn: 8 a (E=P), 8 b (E=As)) can be isolated. Here, a stepwise transfer of En units is possible, with a cyclo-E42− ligand being introduced and unprecedented triple-decker compounds of the type [{(CpRNi)3Ni(μ3-E)4}2(μ,η4:4-E′4)] (CpR=CpBn, Cp′′′; E/E′=P, As) are obtained. 相似文献
13.
Dr. Shenglai Yao M. Sc. Nils Lindenmaier Dr. Yun Xiong Prof. Dr. Shigeyoshi Inoue Dr. Tibor Szilvási Dipl.‐Chem. Mario Adelhardt Dr. Jörg Sutter Prof. Dr. Karsten Meyer Prof. Dr. Matthias Driess 《Angewandte Chemie (International ed. in English)》2015,54(4):1250-1254
The unusual reactivity of the newly synthesized β‐diketiminato cobalt(I) complexes, [(LDepCo)2] ( 2 a , LDep=CH[C(Me)N(2,6‐Et2C6H3)]2) and [LDippCo ? toluene] ( 2 b , LDipp=CH[CHN(2,6‐iPr2C6H3)]2), toward white phosphorus was investigated, affording the first cobalt(I) complexes [(LDepCo)2(μ2:η4,η4‐P4)] ( 3 a ) and [(LDippCo)2(μ2:η4,η4‐P4)] ( 3 b ) bearing the neutral cyclo‐P4 ligand with a rectangular‐planar structure. The redox chemistry of 3 a and 3 b was studied by cyclic voltammetry and their chemical reduction with one molar equivalent of potassium graphite led to the isolation of [(LDepCo)2(μ2:η4,η4‐P4)][K(dme)4] ( 4 a ) and [(LDippCo)2(μ2:η4,η4‐P4)][K(dme)4] ( 4 b ). Unexpectedly, the monoanionic Co2P4 core in 4 a and 4 b , respectively, contains the two‐electron‐reduced cyclo‐P42? ligand with a square‐planar structure and mixed‐valent cobalt(I,II) sites. The electronic structures of 3 a , 3 b , 4 a , and 4 b were elucidated by NMR and EPR spectroscopy as well as magnetic measurements and are in agreement with results of broken‐symmetry DFT calculations. 相似文献
14.
Anthony Cavaillé Dr. Nathalie Saffon‐Merceron Dr. Noel Nebra Dr. Marie Fustier‐Boutignon Dr. Nicolas Mézailles 《Angewandte Chemie (International ed. in English)》2018,57(7):1874-1878
Reduction of the FeII complex [(PhPP2Cy)FeCl2] ( 2 ) generated an electron‐rich and unsaturated Fe0 species, which was reacted with white phosphorus. The resulting new complex, [(PhPP2Cy)Fe(η4‐P4)] ( 3 ), is the first iron cyclo‐P4 complex and the only known stable end‐deck cyclo‐P4 complex outside Group V. Complex 3 features an FeII center, as shown by Mössbauer spectroscopy, associated to a P42? fragment. The distinct reactivity of complex 3 was rationalized by analysis of the molecular orbitals. Reaction of complex 3 with H+ afforded the unstable complex [(PhPP2Cy)Fe(η4‐P4)(H)]+ ( 4 ), whereas with CuCl and BCF, the complexes [(PhPP2Cy)Fe(η4:η1‐P4)(μ‐CuCl)]2 ( 5 ) and [(PhPP2Cy)Fe(η4:η1‐P4)B(C6F5)3] ( 6 ) were formed. 相似文献
15.
Heterometallic Complexes with E6 Ligands (E = P, As) The reaction of [Cp*Co(μ-CO)]2 1 with the sandwich complexes [Cp*Fe(η5-E5)] 2 a: E = P, 2 b: E = As in decalin at 190°C affords besides [CpCo2E4] 4: E = P, 7: E = As and [CpFe2P4] 5 the trinuclear complexes [(Cp*Fe)2(Cp*Co)(μ-η2-P2)(μ3-η1:2:1-P2)2] 3 as well as [(Cp*Fe)2(Cp*Co)(μ3-η2:2:2-As3)2] 6 . With [Mo(CO)5(thf)] 3 and 6 form in a build-up reaction the tetranuclear clusters [(Cp*Fe)2(Cp*Co)E6{Mo(CO)3}] 10: E = P, 11: E = As. 3, 6 and 11 have been further characterized by an X-ray crystal structure determination. 相似文献
16.
Christoph Riesinger Luis Dütsch Dr. Gábor Balázs Dr. Michael Bodensteiner Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(71):17165-17170
The reaction of [Cp′′′Ni(η3-P3)] ( 1 ) with in situ generated phosphenium ions [RR′P]+ yields the unprecedented polyphosphorus cations of the type [Cp′′′Ni(η3-P4R2)][X] (R=Ph ( 2 a ), Mes ( 2 b ), Cy ( 2 c ), 2,2′-biphen ( 2 d ), Me ( 2 e ); [X]−=[OTf]−, [SbF6]−, [GaCl4]−, [BArF]−, [TEF]−) and [Cp′′′Ni(η3-P4RCl)][TEF] (R=Ph ( 2 f ), tBu ( 2 g )). In the reaction of 1 with [Br2P]+, an analogous compound is observed only as an intermediate and the final product is an unexpected dinuclear complex [{Cp′′′Ni}2(μ,η3:η1:η1-P4Br3)][TEF] ( 3 a ). A similar product [{Cp′′′Ni}2(μ,η3:η1:η1-P4(2,2′-biphen)Cl)][GaCl4] ( 3 b ) is obtained, when 2 d [GaCl4] is kept in solution for prolonged times. Although the central structural motif of 2 a – g consists of a “butterfly-like” folded P4 ring attached to a {Cp′′′Ni} fragment, the structures of 3 a and 3 b exhibit a unique asymmetrically substituted and distorted P4 chain stabilised by two {Cp′′′Ni} fragments. Additional DFT calculations shed light on the reaction pathway for the formation of 2 a – 2 g and the bonding situation in 3 a . 相似文献
17.
Dr. Fabian Dielmann Dr. Eugenia V. Peresypkina Barbara Krämer Florian Hastreiter Dr. Brian P. Johnson Dr. Manfred Zabel Dr. Claudia Heindl Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2016,55(47):14833-14837
The cyclo‐P4 complexes [CpRTa(CO)2(η4‐P4)] (CpR: Cp′′=1,3‐C5H3tBu2, Cp′′′=1,2,4‐C5H2tBu3) turned out to be predestined for the formation of hollow spherical supramolecules with non‐classical fullerene‐like topology. The resulting assemblies constructed with CuX (X=Cl, Br) showed a highly symmetric 32‐vertex core of solely four‐ and six‐membered rings. In some supramolecules, the inner cavity was occupied by an additional CuX unit. On the other hand, using CuI, two different supramolecules with either peanut‐ or pear‐like shapes and outer diameters in the range of 2–2.5 nm were isolated. Furthermore, the spherical supramolecules containing Cp′′′ ligands at tantalum are soluble in CH2Cl2. NMR spectroscopic investigations in solution revealed the formation of isomeric supramolecules owing to the steric hindrance caused by the third tBu group on the Cp′′′ ligand. In addition, a 2D coordination polymer was obtained and structurally characterized. 相似文献
18.
Dr. Christoph Schwarzmaier Prof. Dr. Alexey Y. Timoshkin Dr. Gábor Balázs Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2014,53(34):9077-9081
The selective formation of the dinuclear butterfly complexes [{Cp′′′Fe(CO)2}2(μ,η1:1‐E4)] (E=P ( 1 a ), As ( 1 b )) and [{Cp*Cr(CO)3}2(μ,η1:1‐E4)] (E=P ( 2 a ), As ( 2 b )) as new representatives of this rare class of compounds was found by reaction of E4 with the corresponding dimeric carbonyl complexes. Complexes 1 b and 2 b are the first As4 butterfly compounds with a bridging coordination mode. Moreover, first studies regarding the reactivity of 1 b and 2 b are presented, revealing the formation of the unprecedented As8 cuneane complexes [{Cp′′′Fe(CO)2}2{Cp′′′Fe(CO)}2(μ4,η1:1:2:2‐As8)] ( 3 b ) and [{Cp*Cr(CO)3}4(μ4,η1:1:1:1‐As8)] ( 4 ). The compounds are fully characterized by NMR and IR spectroscopy as well as by X‐ray structure analysis. In addition, DFT calculations give insight into the transformation pathway from the E4 butterfly to the corresponding cuneane structural motif. 相似文献
19.
Martin Piesch Dr. Michael Seidl Dr. Markus Stubenhofer Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(25):6311-6316
The reaction of the phosphinidene complex [Cp*P{W(CO)5}2] ( 1 a ) (Cp*=C5Me5) with the anionic cyclo-Pn ligand complex [(η3-P3)Nb(ODipp)3]− ( 2 , Dipp=2,6-diisopropylphenyl) resulted in the formation of [{W(CO)5}2{μ3,η3:1:1-P4Cp*}Nb(ODipp)3]− ( 3 ), which represents an unprecedented example of a ring expansion of a polyphosphorus-ligand complex initiated by a phosphinidene complex. Furthermore, the reaction of the pnictinidene complexes [Cp*E{W(CO)5}2] (E=P: 1 a , As: 1 b ) with the neutral complex [Cp′′′Co(η4-P4)] (Cp′′′=1,2,4-tBu3C5H2) led to a cyclo-P4E ring (E=P, As) through the insertion of the pentel atom into the cyclo-P4 ligand. Starting from 1 a , the two isomers [Cp′′′Co(μ3,η4:1:1-P5Cp*){W(CO)5}2] ( 5 a , b ), and from 1 b , the three isomers [Cp′′′Co(μ3,η4:1:1-AsP4Cp*){W(CO)5}2] ( 6 a – c ) with unprecedented cyclo-P4E ligands (E=P, As) were isolated. The complexes 6 a – c represent unique examples of ring expansions which lead to new mixed five-membered cyclo-P4As ligands. The possible reaction pathways for the formation of 5 a , b and 6 a – c were investigated by a combination of temperature-dependent 31P{1H} NMR studies and DFT calculations. 相似文献
20.
Schindler A Heindl C Balázs G Gröger C Virovets AV Peresypkina EV Scheer M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(3):829-835
Treatment of the pentaphosphaferrocene [Cp*Fe(η5‐P5)] with CuI halides in the presence of different templates leads to novel fullerene‐like spherical molecules that serve as hosts for the templates. If ferrocene is used as the template the 80‐vertex ball [Cp2Fe]@[{Cp*Fe(η5‐P5)}12{CuCl}20] ( 4 ), with an overall icosahedral C80 topological symmetry, is obtained. This result shows the ability of ferrocene to compete successfully with the internal template of the reaction system [Cp*Fe(η5‐P5)], although the 90‐vertex ball [{Cp*Fe(η5:η1:η1:η1:η1:η1‐P5)}12(CuCl)10(Cu2Cl3)5{Cu(CH3CN)2}5] ( 2 a ) containing pentaphosphaferrocene as a guest is also formed as a byproduct. With use of the triple‐decker sandwich complex [(CpCr)2(μ,η5‐As5)] as a template the reaction between [Cp*Fe(η5‐P5)] and CuBr leads to the 90‐vertex ball [(CpCr)2(μ,η5‐As5)]@[{Cp*Fe(η5‐P5)}12{CuBr}10{Cu2Br3}5{Cu(CH3CN)2}5] ( 6 ), in which the complete molecule acts as a template. However, if the corresponding reaction is instead carried out with CuCl, cleavage of the triple‐decker complex is found and the 80‐vertex ball [CpCr(η5‐As5)]@[{Cp*Fe(η5‐P5)}12{CuCl}20] ( 5 ) is obtained. This accommodates as its guest [CpCr(η5‐As5)], which has only 16 valence electrons in a triplet ground state and is not known as a free molecule. The triple‐decker sandwich complex [(CpCr)2(μ,η5‐As5)] requires 53.1 kcal mol?1 to undergo cleavage (as calculated by DFT methods) and therefore this reaction is clearly endothermic. All new products have been characterized by single‐crystal X‐ray crystallography. A favoured orientation of the guest molecules inside the host cages has been identified, which shows π???π stacking of the five‐membered rings (Cp and cyclo‐As5) of the guests and the cyclo‐P5 rings of the nanoballs of the hosts. 相似文献