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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(6):1671-1675
A synthetic approach to the sandwich complex [Cp′′′Co(η4‐P4)] ( 2 ) containing a cyclo‐P4 ligand as an end‐deck was developed. Complex 2 is the missing homologue in the series of first‐row cyclo‐Pn sandwich complexes, and shows a unique tendency to dimerize in solution to form two isomeric P8 complexes [(Cp′′′Co)2(μ,η4:η2:η1‐P8)] ( 3 and 4 ). Reactivity studies indicate that 2 and 3 react with further [Cp′′′Co] fragments to give [(Cp′′′Co)2(μ,η2:η2‐P2)2] ( 5 ) and [(Cp′′′Co)3P8] ( 6 ), respectively. Furthermore, complexes 2 , 3 , and 4 thermally decompose forming 5 , 6 , and the P12 complex [(Cp′′′Co)3P12] ( 7 ). DFT calculations on the P4 activation process suggest a η3‐P4 Co complex as the key intermediate in the synthesis of 2 as well as in the formation of larger polyphosphorus complexes via a unique oligomerization pathway. 相似文献
4.
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
5.
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
6.
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
7.
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
8.
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
9.
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
10.
Christoph Riesinger Prof. Dr. Fabian Dielmann Robert Szlosek Dr. Alexander V. Virovets Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2023,62(16):e202218828
The thermolysis of Cp′′′Ta(CO)4 with white phosphorus (P4) gives access to [{Cp′′′Ta}2(μ,η2 : 2 : 2 : 2 : 1 : 1-P8)] ( A ), representing the first complex containing a cyclooctatetraene-like (COT) cyclo-P8 ligand. While ring sizes of n >6 have remained elusive for cyclo-Pn structural motifs, the choice of the transition metal, co-ligand and reaction conditions allowed the isolation of A . Reactivity investigations reveal its versatile coordination behaviour as well as its redox properties. Oxidation leads to dimerization to afford [{Cp′′′Ta}4(μ4,η2 : 2 : 2 : 2 : 2 : 2 : 2 : 2 : 1 : 1 : 1 : 1-P16)][TEF]2 ( 4 , TEF=[Al(OC{CF3}3)4]−). Reduction, however, leads to the fission of one P−P bond in A followed by rapid dimerization to form [K@[2.2.2]cryptand]2[{Cp′′′Ta}4(μ4,η2 : 2 : 2 : 2 : 2 : 2 : 2 : 2 : 1 : 1 : 1 : 1-P16)] ( 5 ), which features an unprecedented chain-type P16 ligand. Lastly, A serves as a P2 synthon, via ring contraction to the triple-decker complex [{Cp′′′Ta}2(μ,η6 : 6-P6)] ( B ). 相似文献
11.
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
12.
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
13.
Laurence J. Gregoriades Dr. Brian K. Wegley Marek Sierka Dr. Eike Brunner Prof. Dr. Christian Gröger Dr. Eugenia V. Peresypkina Dr. Alexander V. Virovets Dr. Manfred Zabel Dr. Manfred Scheer Prof. Dr. 《化学:亚洲杂志》2009,4(10):1578-1587
The synthesis and characterization of the first supramolecular aggregates incorporating the organometallic cyclo‐P3 ligand complexes [CpRMo(CO)2(η3‐P3)] (CpR=Cp (C5H5; 1a ), Cp* (C5(CH3)5; 1b )) as linking units is described. The reaction of the Cp derivative 1a with AgX (X=CF3SO3, Al{OC(CF3)3}4) yields the one‐dimensional (1D) coordination polymers [Ag{CpMo(CO)2(μ,η3:η1:η1‐P3)}2]n[Al{OC(CF3)3}4]n ( 2 ) and [Ag{CpMo(CO)2(μ,η3:η1:η1‐P3)}3]n[X]n (X=CF3SO3 ( 3a ), Al{OC(CF3)3}4 ( 3b )). The solid‐state structures of these polymers were revealed by X‐ray crystallography and shown to comprise polycationic chains well‐separated from the weakly coordinating anions. If AgCF3SO3 is used, polymer 3a is obtained regardless of reactant stoichiometry whereas in the case of Ag[Al{OC(CF3)3}4], reactant stoichiometry plays a decisive role in determining the structure and composition of the resulting product. Moreover, polymers 3a, b are the first examples of homoleptic silver complexes in which AgI centers are found octahedrally coordinated to six phosphorus atoms. The Cp* derivative 1b reacts with Ag[Al{OC(CF3)3}4] to yield the 1D polymer [Ag{Cp*Mo(CO)2(μ,η3:η2:η1‐P3)}2]n[Al{OC(CF3)3}4]n ( 4 ), the crystal structure of which differs from that of polymer 2 in the coordination mode of the cyclo‐P3 ligands: in 2 , the Ag+ cations are bridged by the cyclo‐P3 ligands in a η1:η1 (edge bridging) fashion whereas in 4 , they are bridged exclusively in a η2:η1 mode (face bridging). Thus, one third of the phosphorus atoms in 2 are not coordinated to silver while in 4 , all phosphorus atoms are engaged in coordination with silver. Comprehensive spectroscopic and analytical measurements revealed that the polymers 2 , 3a , b , and 4 depolymerize extensively upon dissolution and display dynamic behavior in solution, as evidenced in particular by variable temperature 31P NMR spectroscopy. Solid‐state 31P magic angle spinning (MAS) NMR measurements, performed on the polymers 2 , 3b , and 4 , demonstrated that the polymers 2 and 3b also display dynamic behavior in the solid state at room temperature. The X‐ray crystallographic characterisation of 1b is also reported. 相似文献
14.
N‐Functionalized Ferrocenes: Subvalent Group XIV Element Chlorides and tert‐Butyllithium‐Induced C−C Bond Cleavage under Mild Conditions 下载免费PDF全文
Dr. Bastian Nayyar Dr. Hazem Alnasr Prof. Dr. Wolf Hiller Prof. Dr. Klaus Jurkschat 《Angewandte Chemie (International ed. in English)》2018,57(19):5544-5547
The ferrocene derivative (η5‐Cp)Fe{η5‐C5H3‐1‐(ArNCH)‐2‐(CH2NMe2)} ( 1 ; Ar=2,6‐iPr2C6H3)) reacts diastereoselectively with LiR by carbolithiation and subsequent hydrolysis to give (η5‐Cp)Fe{η5‐C5H3‐1‐(ArHNCHR)‐2‐(CH2NMe2)} ( 3 : R=tBu; 4 : R=Ph; 5 : R=Me) in high yields. For R=tBu, the organolithium derivative (η5‐Cp)Fe{η5‐C5H3‐1‐(ArLiNCHR)‐2‐(CH2NMe2)} ( 2 ) was isolated. Compound 2 reacts with GeCl2?dioxane and SnCl2 to give the metallylene amide chlorides (η5‐Cp)Fe{η5‐C5H3‐1‐(ArMNCHtBu)‐2‐(CH2NMe2)} 6 (M=GeCl) and 7 (M=SnCl), respectively, which each contain three stereogenic centers. The potential of 7 as a ligand in transition‐metal chemistry is demonstrated by formation of its complex (η5‐Cp)Fe{η5‐C5H3‐1‐(ArMNCHtBu)‐2‐(CH2NMe2)} [ 9 , M= Sn(Cl)W(CO)5]. Treatment of 3 with tert‐butyllithium at room temperature causes an unprecedented carbon–carbon bond cleavage whereas under kinetic control, lithiation at the Cp‐3 position takes place, which leads to the isolation of (η5‐Cp)Fe{η5‐C5H3‐1‐(ArHNCHtBu)‐2‐(CH2NMe2)‐3‐SiMe3} ( 10 ). 相似文献
15.
Eric Mädl Dr. Mikhail V. Butovskii Dr. Gábor Balázs Dr. Eugenia V. Peresypkina Dr. Alexander V. Virovets Michael Seidl Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2014,53(29):7643-7646
Unprecedented functionalized products with an η4‐P5 ring are obtained by the reaction of [Cp*Fe(η5‐P5)] ( 1 ; Cp*=η5‐C5Me5) with different nucleophiles. With LiCH2SiMe3 and LiNMe2, the monoanionic products [Cp*Fe(η4‐P5CH2SiMe3)]? and [Cp*Fe(η4‐P5NMe2)]?, respectively, are formed. The reaction of 1 with NaNH2 leads to the formation of the trianionic compound [{Cp*Fe(η4‐P5)}2N]3?, whereas the reaction with LiPH2 yields [Cp*Fe(η4‐P5PH2)]? as the main product, with {[Cp*Fe(η4‐P5)]2PH}2? as a byproduct. The calculated energy profile of the reactions provides a rationale for the formation of the different products. 相似文献
16.
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
17.
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
18.
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
19.
Dr. Moritz Modl Dr. Sebastian Heinl Dr. Gabor Balázs Dr. Fuencisla Delgado Calvo Dr. Maria Caporali Dr. Gabriele Manca Martin Keilwerth Prof. Dr. Karsten Meyer Prof. Dr. Maurizio Peruzzini Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(25):6300-6305
The reactivity of ruthenium and manganese complexes bearing intact white phosphorus in the coordination sphere was investigated towards the low-valent transition-metal species [Cp′′′Co] (Cp′′′=η5-C5H2-1,2,4-tBu3) and [L0M] (L0=CH[CHN(2,6-Me2C6H3)]2; M=Fe, Co). Remarkably, and irrespective of the metal species, the reaction proceeds by the selective cleavage of two P–P edges and the formation of a square-planar cyclo-P4 ligand. The reaction products [{CpRu(PPh3)2}{CoCp′′′}(μ,η1:4-P4)][CF3SO3] ( 5 ), [{CpBIGMn(CO)2}2{CoCp′′′}(μ,η1:1:4-P4)] ( 6 ) and [{CpBIGMn(CO)2}2{ML0}(μ,η1:1:4-P4)] (CpBIG=C5(C6H4nBu)5; L0=CH[CHN(2,6-Me2C6H3)]2; M=Fe ( 7 a ), Co ( 7 b )), respectively, were fully characterized by single-crystal X-ray diffraction and spectroscopic methods. The electronic structure of the cyclo-P4 ligand in the complexes 5 – 7 is best described as a π-delocalized P42− system, which is further stabilized by two and three metal moieties, respectively. DFT calculations envisaged a potential intermediate in the reaction to form 5 , in which a quasi-butterfly-shaped P4 moiety bridges the two metals and behaves as an η3-coordinated ligand towards the cobalt center. 相似文献
20.
The Potential of the Diarsene Complex [(C5H5)2Mo2(CO)4(μ,η2-As2)] as a Connector Between Silver Ions
Dr. Mehdi Elsayed Moussa Jana Schiller Dr. Eugenia Peresypkina Dr. Michael Seidl Dr. Gábor Balázs Pavel Shelyganov Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(63):14315-14319
The reaction of the organometallic diarsene complex [Cp2Mo2(CO)4(μ,η2-As2)] ( B ) (Cp = C5H5) with Ag[FAl{OC6F10(C6F5)}3] (Ag[FAl]) and Ag[Al{OC(CF3)3}4] (Ag[TEF]), respectively, yields three unprecedented supramolecular assemblies [(η2- B )4Ag2][FAl]2 ( 4 ), [(μ,η1:η2- B )3(η2- B )2Ag3][TEF]3 ( 5 ) and [(μ,η1:η2- B )4Ag3][TEF]3 ( 6 ). These products are only composed of the complexes B and AgI. Moreover, compounds 5 and 6 are the only supramolecular assemblies featuring B as a linking unit, and the first examples of [AgI]3 units stabilized by organometallic bichelating ligands. According to DFT calculations, complex B coordinates to metal centers through both the As lone pair and the As−As σ-bond thus showing this unique feature of this diarsene ligand. 相似文献