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1.
Niobium and Tantalum Complexes with P2 and P4 Ligands The photolysis of [Cp″Ta(CO)4] 1 (Cp″ = C5H3tBu2?1,3) and P4 affords Cp″(CO)2Ta(η4?P4) 2 , [{Cp″(CO)Ta}2(m??η2:2?P2)2] 3 and [Cp3″(CO)3Ta3(P2)2] 4 . In a photochemical reaction 2 and [Cp*Nb(CO)4] 5 form [{Cp*(CO)Nb}{Cp″(CO)Ta}(m??η2:2?P2)2] 6 and [{Cp*(CO)2Nb} {Cp*Nb}{Cp″(CO)Ta}(m?3?η2:1:1?P2)2] 7 , a compound with the novel m?3?η2:2:1?P2-coordination mode. The reaction of 2 and [Cp*Co(C2H4)2] 8 leads to [{Cp*Co} {Cp″(CO)Ta}(m??η2:2?P2)2] 9 , a heteronuclear complex with an ?early”? and a ?late”? transition metal. Complexes 2, 3, 7 and 9 have been further characterized by X-ray structure analyses. 相似文献
2.
Polynuclear Iron/Tantalum and Tantalum Complexes with Asn Ligands Starting with [Cp@Ta(CO)4] ( 1 ) (Cp@ = C5H3tBu2‐1,3) and As4 or (tBuAs)4 ( 2 ) its thermolysis at 190 °C in decalin gives [{Cp@Ta}2(μ‐η4 : η4‐As8)] ( 3 ), which is also formed according to equation (2) in addition to [{Cp@Ta}3As6] ( 5 ). The reaction of 1 or [{Cp*(OC)2Fe}2] ( 6 ) with 3 affords 5 or [{Cp*Fe}{Cp@Ta}As5] ( 8 ) demonstrating the use of 3 as Asn source. 8 can also be synthesized from 1 and [Cp*Fe(η5‐As5)] ( 7 ) for which the cothermolysis of 2 and 6 gives a better yield. 相似文献
3.
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
4.
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
5.
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
6.
Katarzyna Wójcik Petra Ecorchard Dieter Schaarschmidt Tobias Rüffer Heinrich Lang Prof. Dr. Michael Mehring 《无机化学与普通化学杂志》2012,638(11):1723-1730
Abstract. The cyclopentadienyl‐substituted iron‐bismuth complexes [{Cp(CO)2Fe}BiCl2] ( 1 ), [{Cp(CO)2Fe}BiBr2] ( 2 ), [{Cp′′(CO)2Fe}BiBr2] ( 3 ) and [{Cp*(CO)2Fe}BiBr2] ( 4 ) were prepared with high yields starting from [Cpx(CO)2Fe]2 [Cpx = C5H5 (Cp), C5H3‐1, 3‐tBu2 (Cp′′), C5Me5 (Cp*)] and the corresponding bismuth halides. The single crystal X‐ray structure analyses of compounds 2 – 4 are reported. Comparison of their solubility demonstrates that the steric hindrance in this type of compounds is only slightly higher for compound 3 compared with compound 2 but significantly lower compared with the Cp* derivative 4 . Compounds 1 – 4 react with nucleophililic reagents such as KOtBu, NaOCH2CH2OCH3, and NaOSiMe3 as well as with water in the presence of an amine to give a mixture of [{Cpx(CO)2Fe}BiX] (X = Cl, Br) and [{Cpx(CO)2Fe}3Bi]. In case of a reaction with nBu4NCl and DMAP (dimethylaminopyridine) no such dismutation is observed. Instead the complexes [{Cp(CO)2Fe}BiBr2(DMAP)2] ( 5 ), [NnBu4]2[{{Cp(CO)2Fe}BiBr3}2] ( 6 ) and [NnBu4]2[{{Cp(CO)2Fe}BiCl3}2] ( 7 ) were isolated and characterized by single‐crystal X‐ray diffraction. 相似文献
7.
Manfred Scheer Prof. Dr. Andrea Schindler Dipl.‐Chem. Junfeng Bai Dr. Brian P. Johnson Dr. Roger Merkle Dipl.‐Chem. Rainer Winter Prof. Dr. Alexander V. Virovets Dr. Eugenia V. Peresypkina Dr. Vladislav A. Blatov Prof. Dr. Marek Sierka Dr. Hellmut Eckert Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(7):2092-2107
By applying the proper stoichiometry of 1:2 to [CpRFe(η5‐P5)] and CuX (X=Cl, Br) and dilution conditions in mixtures of CH3CN and solvents like CH2Cl2, 1,2‐Cl2C6H4, toluene, and THF, nine spherical giant molecules having the simplified general formula [CpRFe(η5‐P5)]@[{CpRFe(η5‐P5)}12{CuX}25(CH3CN)10] (CpR=η5‐C5Me5 (Cp*); η5‐C5Me4Et (CpEt); X=Cl, Br) have been synthesized and structurally characterized. The products consist of 90‐vertex frameworks consisting of non‐carbon atoms and forming fullerene‐like structural motifs. Besides the mostly neutral products, some charged derivatives have been isolated. These spherical giant molecules show an outer diameter of 2.24 (X=Cl) to 2.26 nm (X=Br) and have inner cavities of 1.28 (X=Cl) and 1.20 nm (X=Br) in size. In most instances the inner voids of these nanoballs encapsulate one molecule of [Cp*Fe(η5‐P5)], which reveals preferred orientations of π–π stacking between the cyclo‐P5 rings of the guest and those of the host molecules. Moreover, π–π and σ–π interactions are also found in the packing motifs of the balls in the crystal lattice. Electrochemical investigations of these soluble molecules reveal one irreversible multi‐electron oxidation at Ep=0.615 V and two reduction steps (?1.10 and ?2.0 V), the first of which corresponds to about 12 electrons. Density functional calculations reveal that during oxidation and reduction the electrons are withdrawn or added to the surface of the spherical nanomolecules, and no Cu2+ species are involved. 相似文献
8.
Investigations of P–P Bond Formation Reactions in the Coordination Sphere of Transition Metals The reaction of [CpW(CO)3]– with PCl3 leads to the transition metal substituted dichlorphosphines [{CpW(CO)3}PCl2] ( 1 ) and [{Cp(CO)3W}PCl2{WCl(CO)2Cp}] ( 2 ). The X‐ray structure of 2 reveals the Lewis acid/base character of this compound. Reactions of 1 and [Cr(CO)5Cp*PCl2], respectively, with metalates of the type [M(CO)3Cp′]– (M′ = Mo, W; Cp′ = η5‐C5H4tBu) afford the cyclo‐P3 complexes [(η3‐P3)MCp′(CO)3] ( 3 ) (M = W) and ( 4 ) (M = Mo) and the compounds [(μ,η2‐P2{Cr(CO)5}2){Mo(CO)2Cp}2] ( 5 ) and [{μ3‐PW(CO)3Cp′}{W(CO)2Cp′}2] ( 6 ), respectively. Complex 6 possesses a planar homoleptic W3P moiety revealing delocalised multiple bonds within the W2P‐subunit. Reducing [(CO)5WPCl3] with magnesium leads to the formation of the phosphinidene complex [{(CO)5W}2PCl], whereas the reduction of [CpW(CO)3PCl2] ( 1 ) with magnesium yields the cyclo‐P3 complex 3 together with P4 phosphorus. 相似文献
9.
[{Cp″Co}3(μ3-P)(μ3-PSe)], a Trinuclear Cluster with a PSe Ligand The cothermolysis of [Cp″Co(CO)2] ( 1 ), Cp″ = C5H3Bu-1.3, and P4 gives besides [{Cp″Co}3(μ3-P)2] ( 2 ) the cobalt Pn complexes [{Cp″Co}4(μ3-P)4] ( 3 ) and [{Cp″Co}2(μ, η2:2-P2)2] ( 4 ). 2 can be oxidized with grey selenium forming [{Cp″Co}3(μ3-P)(μ3-PSe)] ( 5 ) and [{Cp″Co}3(μ3-PSe)2] ( 6 ), complexes with the hitherto unknown PSe ligand. The crystal structure of 5 reveals a trigonal-bipyramidal Co3P2 skeleton with one μ3-PSe ligand. 相似文献
10.
Masahiro Nagaoka Hiroyuki Tsuruda Dr. Masa‐aki Amako Prof. Dr. Hiroharu Suzuki Prof. Dr. Toshiro Takao 《Angewandte Chemie (International ed. in English)》2015,54(49):14871-14874
A μ3‐η2:η2:η2‐silane complex, [(Cp*Ru)3(μ3‐η2:η2:η2‐H3SitBu)(μ‐H)3] ( 2 a ; Cp*=η5‐C5Me5), was synthesized from the reaction of [{Cp*Ru(μ‐H)}3(μ3‐H)2] ( 1 ) with tBuSiH3. Complex 2 a is the first example of a silane ligand adopting a μ3‐η2:η2:η2 coordination mode. This unprecedented coordination mode was established by NMR and IR spectroscopy as well as X‐ray diffraction analysis and supported by a density functional study. Variable‐temperature NMR analysis implied that 2 a equilibrates with a tautomeric μ3‐silyl complex ( 3 a ). Although 3 a was not isolated, the corresponding μ3‐silyl complex, [(Cp*Ru)3(μ3‐η2:η2‐H2SiPh)(H)(μ‐H)3] ( 3 b ), was obtained from the reaction of 1 with PhSiH3. Treatment of 2 a with PhSiH3 resulted in a silane exchange reaction, leading to the formation of 3 b accompanied by the elimination of tBuSiH3. This result indicates that the μ3‐silane complex can be regarded as an “arrested” intermediate for the oxidative addition/reductive elimination of a primary silane to a trinuclear site. 相似文献
11.
O. J. Scherer J. Meiers M. Regitz M. A. Hofmann K. Karaghiosoff G. Wolmershuser 《无机化学与普通化学杂志》2001,627(7):1532-1536
[CpR(OC)Mo(μ‐η2:2‐P2)2FeCpR′] as Educt for Heterobimetallic Dinuclear Clusters with P2 and CnRnP4‐n Ligands (n = 1, 2) The cothermolysis of [CpR(OC)Mo(μ‐η2:2‐P2)2FeCpR′] ( 1 ) and tBuC≡P ( 2 ) as well as PhC≡CPh ( 3 ) affords the heterobimetallic triple‐decker like dinuclear clusters [(Cp'''Mo)(Cp*′Fe)(P3CtBu)(P2)] ( 4 ), Cp''' = C5H2tBu3‐1,2,4, Cp*′ = C5Me4Et, and [(Cp*Mo)(Cp*Fe)(P2C2Ph2)(P2)] ( 5 ) with a bridging tri‐ and diphosphabutadiendiyl ligand. 4 and 5 have been characterized additionally by X‐ray crystallography. 相似文献
12.
Molecular and Crystal Structure of Bis[chloro(μ‐phenylimido)(η5‐pentamethylcyclopentadienyl)tantalum(IV)](Ta–Ta), [{TaCl(μ‐NPh)Cp*}2] Despite the steric hindrance of the central atom in [TaCl2(NPh)Cp*] (Ph = C6H5, Cp* = η5‐C5(CH3)5), caused by the Cp* ligand, the imido‐ligand takes a change in bond structure when this educt is reduced to the binuclear complex [{TaCl(μ‐NPh)Cp*}2] in which tantalum is stabilized in the unusual oxidation state +4. 相似文献
13.
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes XXI The Influence of the PR3 Ligands on Formation and Properties of the Phosphinophosphinidene Complexes [{η2‐tBu2P–P}Pt(PR3)2] and [{η2‐tBu2P1–P2}Pt(P3R3)(P4R′3)] (R3P)2PtCl2 and C2H4 yield the compounds [{η2‐C2H4}Pt(PR3)2] (PR3 = PMe3, PEt3, PPhEt2, PPh2Et, PPh2Me, PPh2iPr, PPh2tBu and P(p‐Tol)3); which react with tBu2P–P=PMetBu2 to give the phosphinophosphinidene complexes [{η2‐tBu2P–P}Pt(PMe3)2], [{η2‐tBu2P–P}Pt(PEt3)2], [{η2‐tBu2P–P}Pt(PPhEt2)2], [{η2‐tBu2P–P}Pt(PPh2Et)2], [{η2‐tBu2P–P}Pt(PPh2Me)2], [{η2‐tBu2P–P}Pt(PPh2iPr], [{η2‐tBu2P–P}Pt(PPh2tBu)2] and [{η2‐tBu2P–P}Pt(P(p‐Tol)3)2]. [{η2‐tBu2P–P}Pt(PPh3)2] reacts with PMe3 and PEt3 as well as with tBu2PMe, PiPr3 and P(c‐Hex)3 by substituting one PPh3 ligand to give [{η2‐tBu2P1–P2}Pt(P3Me3)(P4Ph3)], [{η2‐tBu2P1–P2}Pt(P3Ph3)(P4Me3)], [{η2‐tBu2P1–P2}Pt(P3Et3)(P4Ph3)], [{η2‐tBu2P1–P2}Pt(P3MetBu2)(P4Ph3)], [{η2‐tBu2P1–P2}Pt(P3iPr3)(P4Ph3)] and [{η2‐tBu2P1–P2}Pt(P3(c‐Hex)3)(P4Ph3)]. With tBu2PMe, [{η2‐tBu2P–P}Pt(P(p‐Tol)3)2] forms [{η2‐tBu2P1–P2}Pt(P3MetBu2)(P4(p‐Tol)3)]. The NMR data of the compounds are given and discussed with respect to the influence of the PR3 ligands. 相似文献
14.
Reaction of Pentelidene Complexes with Diazoalkanes: Stabilization of Parent 2,3‐Dipnictabutadienes 下载免费PDF全文
Dr. Michael Seidl Dr. Markus Stubenhofer Prof. Dr. Alexey Y. Timoshkin Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2016,55(45):14037-14040
The reaction of the phosphinidene complex [Cp*P{W(CO)5}2] ( 1 a ) with diphenyldiazomethane leads to [{W(CO)5}Cp*P=NN{W(CO)5}=CPh2] ( 2 ). Compound 2 is a rare example of a phosphadiazadiene ligand (R‐P=N?N=CR′R′′) complex. At temperatures above 0 °C, 2 decomposes into the complex [{W(CO)5}PCp*{N(H)N=CPh2)2] ( 3 ), among other species. The reaction of the pentelidene complexes [Cp*E{W(CO)5}2] (E=P, As) with diazomethane (CH2NN) proceeds differently. For the arsinidene complex ( 1 b ), only the arsaalkene complex 4 b [{W(CO)5}2{η1:2‐(Cp*)As=CH2}] is formed. The reaction with the phosphinidene complex ( 1 a ) results in three products, the two phosphaalkene complexes [{W(CO)5}2{η1:2‐(R)P=CH2}] ( 4 a : R=Cp*, 5 : R=H) and the triazaphosphole derivative [{W(CO)5}P(Cp*)‐CH2‐N{W(CO)5}=N‐N(N=CH2)] ( 6 a ). The phosphaalkene complex ( 4 a ) and the arsaalkene complex ( 4 b ) are not stable at room temperature and decompose to the complexes [{W(CO)5}4(CH2=E?E=CH2)] ( 7 a : E=P, 7 b : E=As), which are the first examples of complexes with parent 2,3‐diphospha‐1,3‐butadiene and 2,3‐diarsa‐1,3‐butadiene ligands. 相似文献
15.
Jana Schiller Eugenia Peresypkina Alexander V. Virovets Manfred Scheer 《Angewandte Chemie (International ed. in English)》2020,59(32):13647-13650
An unprecedented cationic supramolecule [(Cp′′Fe(η5‐P5))12{CuNCMe}8]8+ 2.66 nm in diameter was selectively isolated as a salt of the weakly coordinating anion [Al{OC(CF3)3}4]? for the first time and characterized by X‐ray structure analysis, PXRD, NMR spectroscopy, and mass spectrometry. Its metal‐deficient core contains the lowest possible number of Cu atoms to connect 12 pentaphosphaferrocene units, providing a supramolecule with fullerene topology which, topologically, also represents the simplest homologue in the family of metal‐deficient pentaphosphaferrocene‐based supramolecules [{CpRFe(η5‐P5)}12(CuX)20?n]. The 12 vacant metal sites between the cyclo‐P5 rings, the largest number attained to date, make this compound a facile precursor for potential inner and outer modifications of the core as well as for functionalization via the substitution of labile acetonitrile ligands. 相似文献
16.
Matthias Stender Hannes Oesen Steffen Blaurock Evamarie Hey‐Hawkins 《无机化学与普通化学杂志》2001,627(5):980-984
Synthesis and Molecular Structure of [{Cp′(μ‐η1 : η5‐C5H3Me)Mo(μ‐AlRH)}2] (Cp′ = C5H4Me, R = iBu, Et) [Cp′2MoH2] reacts with HAlR2 to give [{Cp′(μ‐η1 : η5‐C5H3Me)Mo(μ‐AlRH)}2] (Cp′ = C5H4Me, R = iBu ( 1 ), Et ( 2 )). Crystal structure determinations were carried out on [Cp′2MoH2] and 1 . 1 exhibits a direct Mo–Al bond (2.636(2) Å). 相似文献
17.
Dr. Michael Seidl Dr. Gábor Balázs Prof. Dr. Alexey Y. Timoshkin Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2016,55(1):431-435
The reaction of the phosphinidene complex [Cp*P{W(CO)5}2] ( 1 a ) with di‐tert‐butylcarboimidophosphene leads to the P? C cage compound 6 and the Lewis acid–base adduct [Cp*P{W(CO)5}2(CNtBu)] ( 2 a ). In contrast, the arsinidene complex shows a different reactivity. At low temperatures, the arsaphosphene complex [{W(CO)5}{η2‐(Cp*)As?P(tBu)}{W(CO)5}] ( 3 ) is formed. At these temperatures, 3 reacts further with a second equivalent of carboimidophosphene to form [{W(CO)5}{η2‐{(Cp*)(tBu)P}As?P(tBu)}{W(CO)5}] ( 5 ), probably by the insertion of a phosphinidene unit (tBuP) into an As? C bond. In contrast, at room temperature 3 reacts further by a radical‐type reaction to form [{(tBu)P?As? As?P(tBu)}{W(CO)5}4] ( 4 ). Compound 4 is the first example of a neutral, 1,3‐butadiene analogue containing only mixed heavier Group 15 elements. It consists of two P?As double bonds connected by arsenic atoms. 相似文献
18.
Martin Fleischmann Dr. Stefan Welsch Dr. Eugenia V. Peresypkina Dr. Alexander V. Virovets Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(41):14332-14336
Reactions of Cu+ containing the weakly coordinating anion [Al{OC(CF3)3}4]? with the polyphosphorus complexes [{CpMo(CO)2}2(μ,η2:η2‐P2)] ( A ), [CpM(CO)2(η3‐P3)] (M=Cr( B1 ), Mo ( B2 )), and [Cp*Fe(η5‐P5)] ( C ) are presented. The X‐ray structures of the products revealed mononuclear ( 4 ) and dinuclear ( 1 , 2 , 3 ) CuI complexes, as well as the one‐dimensional coordination polymer ( 5 a ) containing an unprecedented [Cu2( C )3]2+ paddle‐wheel building block. All products are readily soluble in CH2Cl2 and exhibit fast dynamic coordination behavior in solution indicated by variable temperature 31P{1H} NMR spectroscopy. 相似文献
19.
Carolin Albrecht Thomas Krüger Christoph Wagner Tobias Rüffer Heinrich Lang Dirk Steinborn Prof. Dr. 《无机化学与普通化学杂志》2008,634(14):2495-2503
On the Reactivity of Titanocene Complexes [Ti(Cp′)2(η2‐Me3SiC≡CSiMe3)] (Cp′ = Cp, Cp*) towards Benzenedicarboxylic Acids Titanocene complexes [Ti(Cp′)2(BTMSA)] ( 1a , Cp′ = Cp = η5‐C5H5; 1b , Cp′ = Cp* = η5‐C5Me5; BTMSA = Me3SiC≡CSiMe3) were found to react with iodine and methyl iodide yielding [Ti(Cp′)2(μ‐I)2] ( 2a / b ; a refers to Cp′ = Cp and b to Cp′ = Cp*), [Ti(Cp′)2I2] ( 3a / b ) and [Ti(Cp′)2(Me)I] ( 4a / b ), respectively. In contrast to 2a , complex 2b proved to be highly moisture sensitive yielding with cleavage of HCp* [{Ti(Cp*)I}2(μ‐O)] ( 7 ). The corresponding reactions of 1a / b with p‐cresol and thiophenol resulted in the formation of [Ti(Cp′)2{O(p‐Tol)}2] ( 5a / b ) and [Ti(Cp′)2(SPh)2] ( 6a / b ), respectively. Reactions of 1a and 1b with 1,n‐benzenedicarboxylic acids (n = 2–4) resulted in the formation of dinuclear titanium(III) complexes of the type [{Ti(Cp′)2}2{μ‐1,n‐(O2C)2C6H4}] (n = 2, 8a / b ; n = 3, 9a / b ; n = 4, 10a / b ). All complexes were fully characterized analytically and spectroscopically. Furthermore, complexes 7 , 8b , 9a ·THF, 10a / b were also be characterized by single‐crystal X‐ray diffraction analyses. 相似文献
20.
Ravi Yadav Thomas Simler Bhupendra Goswami Christoph Schoo Ralf Kppe Subhayan Dey Peter W. Roesky 《Angewandte Chemie (International ed. in English)》2020,59(24):9443-9447
A route to directly access mixed Al–Fe polyphosphide complexes was developed. The reactivity of pentaphosphaferrocene, [Cp*Fe(η5‐P5)] (Cp*=C5Me5), with two different low‐valent aluminum compounds was investigated. The steric and electronic environment around the [AlI] centre are found to be crucial for the formation of the resulting Al–Fe polyphosphides. Reaction with the sterically demanding [Dipp‐BDIAlI] (Dipp‐BDI={[2,6‐iPr2C6H3NCMe]2CH}?) resulted in the first Al‐based neutral triple‐decker type polyphosphide complex. For [(Cp*AlI)4], an unprecedented regioselective insertion of three [Cp*AlIII]2+ moieties into two adjacent P?P bonds of the cyclo‐P5 ring of [Cp*Fe(η5‐P5)] was observed. The regioselectivity of the insertion reaction could be rationalized by isolating an analogue of the reaction intermediate stabilized by a strong σ‐donor carbene. 相似文献