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1.
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
2.
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
3.
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
4.
Dr. Rebecca Grünbauer Dr. Gábor Balázs Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(51):11722-11726
The versatile coordination behavior of the P4 butterfly complex [{Cp*Cr(CO)3}2(μ,η1:1-P4)] ( 1 ) towards Lewis acidic pentacarbonyl compounds of Cr, Mo and W is reported. The reaction of 1 with [W(CO)4(nbd)] (nbd=norbornadiene) yields the complex [{Cp*Cr(CO)3}2(μ3,η1:1:1:1-P4){W(CO)4}] ( 2 ) in which 1 serves as a chelating P4 butterfly ligand. In contrast, reactions of 1 with [M(CO)4(nbd)] (M=Cr ( a ), Mo ( b )) result in the step-wise formation of [{Cp*Cr(CO)2}2(μ3,η3:1:1-P4){M(CO)5}] ( 3 a,b ) and [{Cp*Cr(CO)2}2-(μ4,η3:1:1:1-P4){M(CO)5}2] ( 4 a,b ) which contain a folded cyclo-P4 unit. Complex 4 a undergoes an unprecedented P1/P3-fragmentation yielding the cyclo-P3 complex [Cp*Cr(CO)2(η3-P3)] ( 5 ) and the as yet unknown phosphinidene complex [Cp*Cr(CO)2{Cr(CO)5}2(μ3-P)] ( 6 ). The identity of 6 is confirmed by spectroscopic methods and by the in situ formation of [{Cp*Cr(CO)2(tBuNC)}P{Cr(CO)5}2(tBuNC)] ( 7 ). DFT calculations throw light on the bonding situation of the reported products. 相似文献
5.
Reaction of Tungsten–Phosphinidene and –Arsinidene Complexes with Carbodiimides and Alkyl Azides: A Straightforward Way to Four‐Membered Heterocycles 下载免费PDF全文
Michael Seidl Dr. Christian Kuntz Dr. Michael Bodensteiner Prof. Dr. Alexey Y. Timoshkin Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2015,54(9):2771-2775
The reaction of the phosphinidene and arsinidene complexes [Cp*E{W(CO)5}2] (E=P ( 1 a ), As ( 1 b ); Cp*=C5Me5) with carbodiimides leads to the new four‐membered heterocycles of the type [Cp*C(NR)2E{W(CO)5}2] (E=P: R=iPr ( 2 a ), Cy ( 3 a ); E=As: R=iPr ( 2 b ), Cy ( 3 b )). The reaction of phosphinidene complex 1 a with alkyl azides yields the triazaphosphete derivatives [Cp*P{W(CO)5}N(R)NN{W(CO)5}] (R=Hex, Cy) ( 4 ). These unprecedented N3P four‐membered triazaphosphete complexes can be regarded as stabilized intermediates of the Staudinger reaction, which have not been previously isolated. All of the isolated products were characterized by NMR, IR spectroscopy, mass spectrometry, and by single‐crystal X‐ray diffraction analysis. 相似文献
6.
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
7.
Synthesis,Structure, Bonding,and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] and [{Cp*M(CO)2}2B2H2M(CO)4], M=Mo,W 下载免费PDF全文
Dr. Bijan Mondal Ranjit Bag Sagar Ghorai Dr. K. Bakthavachalam Prof. Eluvathingal D. Jemmis Prof. Sundargopal Ghosh 《Angewandte Chemie (International ed. in English)》2018,57(27):8079-8083
The reaction of [(Cp*Mo)2(μ‐Cl)2B2H6] ( 1 ) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] ( 2 ). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged Cs structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum–alkyne complex [{CpMo(CO)2}2C2H2]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO)4] fragment, [{Cp*Mo(CO)2}2 B2H2W(CO)4] ( 3 ) was isolated upon treatment with [W(CO)5?thf]. Compound 3 shows the intriguing presence of [B2H2] with a short B?B length of 1.624(4) Å. We isolated the tungsten analogues of 3 , [{Cp*W(CO)2}2B2H2W(CO)4] ( 4 ) and [{Cp*W(CO)2}2B2H2Mo(CO)4] ( 5 ), which provided direct proof of the existence of the tungsten analogue of 2 . 相似文献
8.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2018,130(27):8211-8215
The reaction of [(Cp*Mo)2(μ‐Cl)2B2H6] ( 1 ) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] ( 2 ). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged Cs structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum–alkyne complex [{CpMo(CO)2}2C2H2]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO)4] fragment, [{Cp*Mo(CO)2}2 B2H2W(CO)4] ( 3 ) was isolated upon treatment with [W(CO)5⋅thf]. Compound 3 shows the intriguing presence of [B2H2] with a short B−B length of 1.624(4) Å. We isolated the tungsten analogues of 3 , [{Cp*W(CO)2}2B2H2W(CO)4] ( 4 ) and [{Cp*W(CO)2}2B2H2Mo(CO)4] ( 5 ), which provided direct proof of the existence of the tungsten analogue of 2 . 相似文献
9.
Mehdi ElsayedMoussa Michael Seidl Gbor Balzs Matthias Hautmann Manfred Scheer 《Angewandte Chemie (International ed. in English)》2019,58(37):12903-12907
The reactions of tetrahedral molybdenum complexes bearing unsubstituted heterodiatomic Group 15 elements, [Cp2Mo2(CO)4(μ,η2:η2‐PE)] (Cp=C5H5; E=As ( 1 ), Sb ( 2 )), with CuI halides afforded seven unprecedented neutral supramolecular assemblies. Depending on the Mo2PE units and the CuI halide, the oligomers [?{Cp2Mo2(CO)4}{μ4,η2:η2:η2:η1‐PE}?4?{CuX}{Cu(μ‐X)}?2] (E=As (X=Cl ( 3 ), Br ( 4 )); E=Sb (X=Cl ( 6 ), Br ( 7 ))) or the 1D coordination polymers [{Cp2Mo2(CO)4}{μ4,η2:η2:η1:η1‐PAs}{Cu(μ‐I)}]n ( 5 ) and [{Cp2Mo2(CO)4}{μ4,η2:η2:η2:η1‐PSb}2{Cu(μ‐X)}3]n (X=I ( 8 ), Br ( 9 )) are accessible. These solid‐state aggregates are the first and only examples featuring the organometallic heterodiatomic Mo2PE complexes 1 and 2 as linking moieties. DFT calculations demonstrate that complexes 1 and 2 present a unique class of mixed‐donor ligands coordinating to CuI centers via the P lone pair and the P?E σ‐bond, revealing an unprecedented coordination mode. 相似文献
10.
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
11.
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
12.
Reinhard Rund Gbor Balzs Michael Bodensteiner Manfred Scheer 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(45):16238-16242
The terminal diarsene HAs=AsH ligand attracts special interest concerning its bonding relation in comparison to its isolable relative, ethene. Herein, by the methanolysis of [{Fe(CO)4}As(SiMe3)3] ( 1 ) the synthesis of [{Fe(CO)4}(η2‐As2H2)] ( 2 ) is reported, containing a parent diarsene as unprecedented side‐on coordinated ligand. Following this synthetic route, also the D‐labeled complex [{Fe(CO)4}(η2‐As2D2)] ( 2D ) could be isolated. The electronic structure and bonding situation of 2 was elucidated by DFT calculations revealing that 2 is best described as an olefin‐like complex. Moreover, the reactivity of 2 towards the Lewis acids [{M(CO)5}(thf)] (M=Cr, W) was investigated, leading to the complexes [Fe(CO)4AsHW(CO)5]2 ( 3 ) and [{Fe(CO)4}2AsH{Cr(CO)5}] ( 4 ), respectively. 相似文献
13.
Dr. Michael Seidl Rudolf Weinzierl Prof. Dr. Alexey Y. Timoshkin Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5484-5488
The phosphinidene complex [Cp*P{W(CO)5}2] ( 1 ; Cp*=C5Me5) reacted with malononitrile to give the 1,2‐dihydro‐1,3,2‐diazaphosphinine derivative 2 . The reaction of 1 with 1,4‐benzodinitrile gave [1,4‐{{W(CO)5}2P‐N=C(Cp*)}2(C6H4)] ( 3 ), the first example of a cumulene‐like aminophosphinidene complex. The reaction of 1 with aniline gave the aminophosphinidene complex [(Ph)N(H)P{W(CO)5}2] ( 4 ). To compare the reactivity of benzonitrile and aniline with 1 , the phosphinidene complex 1 was reacted with three different isomers of aminobenzonitrile (2‐, 3‐, and 4‐aminobenzonitrile). These reactions gave an insight into the reaction pathway of 1 with benzonitrile derivatives. Compounds 5 , 6 a , 6 b , and 7 , which are derivatives of 1,2‐dihydro‐1,3,2‐diazaphosphinine or benzo‐2H‐1,2‐azaphospholes, were, as well as all other products, characterized by mass spectrometry, NMR and IR spectroscopy, and X‐ray structure analysis. 相似文献
14.
Markus Stubenhofer Dipl.‐Chem. Christian Kuntz Dr. Michael Bodensteiner Dipl.‐Chem. Ulrich Zenneck Prof. Dr. Marek Sierka Dr. Manfred Scheer Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(25):7488-7495
Photolysis of [Cp*As{W(CO)5}2] ( 1 a ) in the presence of Mes*P?PMes* (Mes*=2,4,6‐tri‐tert‐butylphenyl) leads to the novel 1,3‐diphospha‐2‐arsaallyl radical [(CO)5W(μ,η2:η1‐P2AsMes*2)W(CO)4] ( 2 a ). The frontier orbitals of the radical 2 a are indicative of a stable π‐allylic system that is only marginally influenced by the d orbitals of the two tungsten atoms. The SOMO and the corresponding spin density distribution of the radical 2 a show that the unpaired electron is preferentially located at the two equivalent terminal phosphorus atoms, which has been confirmed by EPR spectroscopy. The protonated derivative of 2 a , the complex [(CO)5W(μ,η2:η1‐P2As(H)Mes*2)W(CO)4] ( 6 a ) is formed during chromatographic workup, whereas the additional products [Mes*P?PMes*{W(CO)5}] as the Z‐isomer ( 3 ) and the E‐isomer ( 4 ), and [As2{W(CO)5}3] ( 5 ) are produced as a result of a decomposition reaction of radical 2 a . Reduction of radical 2 a yields the stable anion [(CO)5W(μ,η2:η1‐P2AsMes*2)W(CO)4]? in 7 a , whereas upon oxidation the corresponding cationic complex [(CO)5W(μ,η2:η1‐P2AsMes*2)W(CO)4][SbF6] ( 8 a ) is formed, which is only stable at low temperatures in solution. Compounds 2 a , 7 a , and 8 a represent the hitherto elusive complexed redox congeners of the diphospha‐arsa‐allyl system. The analogous oxidation of the triphosphaallyl radical [(CO)5W(μ,η2:η1‐ P3Mes*2)W(CO)4] ( 2 b ) also leads to an allyl cation, which decomposes under CH activation to the phosphine derivative [(CO)5W{μ,η2:η1‐P3(Mes*)(C5H2tBu2C(CH3)2CH2)}W(CO)4] ( 9 ), in which a CH bond of a methyl group of the Mes* substituent has been activated. All new products have been characterized by NMR spectrometry and IR spectroscopy, and compounds 2 a , 3 , 6 a , 7 a , and 9 by X‐ray diffraction analysis. 相似文献
15.
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
16.
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
17.
Guido Schmitt Dietmar Ullrich Gotthelf Wolmershuser Manfred Regitz Otto J. Scherer 《无机化学与普通化学杂志》1999,625(5):702-704
tBuC≡P as a Synthon for the Formation of a Dinuclear Rhenium Complex with a Bridging and Chiral Phosphinidene Oxide Ligand The one‐pot reaction of [{Cp*(OC)2Re}2] (Re = Re) ( 3 ) with tBuC≡P ( 4 ) and the subsequent oxidation with (Me3Si)2O2 ( 5 ) affords [Re(CO)2C5Me4CH2{μ‐HC(But)P(O)}Re(CO)2Cp*] ( 6 ), a dinuclear rhenium complex with a bridging and chiral phosphinidene oxide ligand. Its structure was confirmed by an X‐ray crystal structure determination. 相似文献
18.
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
19.
Experimental and Computational Studies on the Reactivity of a Terminal Thorium Imidometallocene towards Organic Azides and Diazoalkanes 下载免费PDF全文
Dr. Wenshan Ren Enwei Zhou Bo Fang Dr. Guohua Hou Prof. Guofu Zi Prof. De‐Cai Fang Dr. Marc D. Walter 《Angewandte Chemie (International ed. in English)》2014,53(42):11310-11314
The reaction of the base‐free terminal thorium imido complex [{η5‐1,2,4‐(Me3C)3C5H2}2Th?N(p‐tolyl)] ( 1 ) with p‐azidotoluene yielded irreversibly the tetraazametallacyclopentene [{η5‐1,2,4‐(Me3C)3C5H2}2Th{N(p‐tolyl)N?N? N(p‐tolyl)}] ( 2 ), whereas the bridging imido complex [{[η5‐1,2,4‐(Me3C)3C5H2]Th(N3)2}2{μ‐N(p‐tolyl)}2][(n‐C4H9)4N]2 ( 3 ) was isolated from the reaction of 1 with [(n‐C4H9)4N]N3. Unexpectedly, upon the treatment of 1 with 9‐diazofluorene, the NN bond was cleaved, an N atom was transferred, and the η2‐diazenido iminato complex [{η5‐1,2,4‐(Me3C)3C5H2}2Th{η2‐[N?N(p‐tolyl)]}{N?(9‐C13H8)}] ( 4 ) was formed. In contrast, the reaction of 1 with Me3SiCHN2 gave the nitrilimido complex [{η5‐1,2,4‐(Me3C)3C5H2}2Th{NH(p‐tolyl)}{N2CSiMe3}] ( 5 ), which slowly converted into [{η5‐1,2,4‐(Me3C)3C5H2}{η5:κ‐N‐1,2‐(Me3C)2‐4‐CMe2(CH2NN?CHSiMe3)C5H2}Th{NH(p‐tolyl)}] ( 6 ) by intramolecular C? H bond activation. The experimental results are complemented by density functional theory (DFT) studies. 相似文献
20.
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