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1.
Fengying Zhou Suyun Zhang Yang Zhao Chongguang Zhang Xiaojuan Cheng Lina Zheng Yong Zhang Yahong Li Prof. Dr. 《无机化学与普通化学杂志》2009,635(15):2636-2641
Reaction of DyCl3 with two equivalents of NaN(SiMe3)2 in THF yielded {Dy(μ‐Cl)[N(SiMe3)2]2(THF)}2 ( 1 ). X‐ray crystal structure analysis revealed that 1 is a centrosymmetric dimer with asymmetrically bridging chloride ligands. The metal coordination arrangement can be best described as distorted trigonal bipyramid. The bond lengths of Ln–Cl and Ln–N showed a decreasing trend with the contraction of the size of Ln3+. Treatment of N,N‐bis(pyrrolyl‐α‐methyl)‐N‐methylamine (H2dpma) with 1 and known compound {Yb(μ‐Cl)[N(SiMe3)2]2(THF)}2, respectively, led to the formations of [Dy(μ‐Cl)(dpma)(THF)2]2 ( 2 ) and {Yb(μ‐Cl)[N(SiMe3)2]2(THF)}2 ( 3 ). Compounds 2 and 3 were fully characterized by single‐crystal X‐ray crystallography, elemental analysis, and 1H NMR spectroscopy. Structure determination indicated that 2 and 3 exhibit as centrosymmetric dimers with asymmetrically bridging chloride ligands. One pot reactions involving LnCl3 (Ln = Dy and Yb), LiN(SiMe3)2, and H2dpma were explored and desired products 2 and 3 were not yielded, which indicated that 1 and {Yb(μ‐Cl)[N(SiMe3)2]2(THF)}2 are the demanding precursors to synthesize Dysprosium and Ytterbium complexes supported by dpma2– ligand. Compounds 2 and 3 are the first reported lanthanide complexes chelated by dpma2– ligand. 相似文献
2.
Jan Keuter Alexander Hepp Christian Mück‐Lichtenfeld Felicitas Lips 《Angewandte Chemie (International ed. in English)》2019,58(13):4395-4399
Reaction of the bicyclo[1.1.0]tetrasilatetraamide Si4{N(SiMe3)Dipp}4 1 (Dipp=2,6‐diisopropylphenyl) with 5 equiv of the N‐heterocyclic carbene NHCMe4 (1,3,4,5‐tetramethylimidazol‐2‐ylidene) affords a bifunctional carbene‐coordinated four‐membered‐ring compound with a Si=N group and a two‐coordinate silicon atom Si4{N(SiMe3)Dipp}2(NHCMe4)2(NDipp) 2 . When 2 reacts with 0.25 equiv sulfur (S8), two sulfur atoms add to the divalent silicon atom in plane and perpendicular to the plane of the Si4 ring, which confirms the silylone character of the two‐coordinate silicon atom in 2 . 相似文献
3.
Samuel Grams Jonathan Eyselein Jens Langer Christian Frber Sjoerd Harder 《Angewandte Chemie (International ed. in English)》2020,59(37):15982-15986
The reagent RK [R=CH(SiMe3)2 or N(SiMe3)2] was expected to react with the low‐valent (DIPPBDI)Al (DIPPBDI=HC[C(Me)N(DIPP)]2, DIPP=2,6‐iPr‐phenyl) to give [(DIPPBDI)AlR]?K+. However, deprotonation of the Me group in the ligand backbone was observed and [H2C=C(N‐DIPP)?C(H)=C(Me)?N?DIPP]Al?K+ ( 1 ) crystallized as a bright‐yellow product (73 %). Like most anionic AlI complexes, 1 forms a dimer in which formally negatively charged Al centers are bridged by K+ ions, showing strong K+???DIPP interactions. The rather short Al–K bonds [3.499(1)–3.588(1) Å] indicate tight bonding of the dimer. According to DOSY NMR analysis, 1 is dimeric in C6H6 and monomeric in THF, but slowly reacts with both solvents. In reaction with C6H6, two C?H bond activations are observed and a product with a para‐phenylene moiety was exclusively isolated. DFT calculations confirm that the Al center in 1 is more reactive than that in (DIPPBDI)Al. Calculations show that both AlI and K+ work in concert and determines the reactivity of 1 . 相似文献
4.
Lithium bis(trimethylsilyl)amide, LiN(SiMe3)2, reacts with Cp*V(O)Cl2 and Cp*TaCl4 to give trimethylsilylimido complexes such as [Cp*V(NSiMe3)(μ‐NSiMe3)]2 ( 7 ) and Cp*Ta(Cl)(NSiMe3)[N(SiMe3)2] ( 19 ), respectively. Substitution of the chloro ligand in 19 by anionic groups leads to complexes with 3 different N‐containing ligands, Cp*Ta(X)(NSiMe3)[N(SiMe3)2] (X = N3 ( 20 ) or NPEt3 ( 21 )). Complex 7 is air‐ and moisture‐sensitive, and several derivatives containing oxo and trimethylsiloxy ligands have been identified. Trimethylsilyl azide, Me3Si‐N3, is able to replace the oxygen‐containing ligands for azido ligands. The two complete series of bis(azido)‐bridged complexes, [Cp*VCln(N3)2‐n(μ‐N3)]2 (n = 2, 1, 0) and [Cp*TaCln(N3)3‐n(μ‐N3)]2(n = 3, 2, 1, 0), are accessible from the reactions of Cp*VCl3 and Cp*TaCl4, respectively, with trimethylsilyl azide. A bis(nitrido)‐bridged azido‐vanadium complex, [Cp*V(N3)(μ‐N)]2 ( 18 ), has also been obtained and structurally characterized. 相似文献
5.
1,2‐Diaza‐3‐silacyclopent‐5‐ene – Synthesis and Reactions The dilithium salt of bis(tert‐butyl‐trimethylsilylmethylen)ketazine ( 1 ) forms an imine‐enamine salt. 1 reacts with halosilanes in a molar ratio of 1:1 to give 1,2‐diaza‐3‐silacyclopent‐5‐enes. Me3SiCH=CCMe3 [N(SiR,R′)‐N=C‐C]HSiMe3 ( 2 ‐ 7 ). ( 2 : R,R′ = Cl; 3 : R = CH3, R′ = Ph; 4 : R = F, R′ = CMe3; 5 : R = F, R′ = Ph; 6 : R = F, R′ = N(SiMe3)2; 7 : R = F, R′ = N(CMe3)SiMe3). In the reaction of 1 with tetrafluorosilane the spirocyclus 8 is isolated. The five‐membered ring compounds 2 ‐ 7 and compound 9 substituted on the silicon‐fluoro‐ and (tert‐butyltrimethylsilyl) are acid at the C(4)‐atom and therefore can be lithiated. Experiments to prepare lithium salts of 4 with MeLi, n‐BuLi and PhLi gave LiF and the substitution‐products 10 ‐ 12 . 9 forms a lithium salt which reacts with ClSiMe3 to give LiCl and the SiMe3 ring system ( 13 ) substituted at the C(4)‐atom. The ring compounds 3 ‐ 7 and 10 ‐ 12 form isomers, the formation is discussed. Results of the crystal structure and analyses of 8 , 10 , 12 , and 13 are presented. 相似文献
6.
Stephan Gießmann Steffen Blaurock Anja Edelmann Volker Lorenz Frank T. Edelmann Prof. Dr. 《无机化学与普通化学杂志》2008,634(14):2459-2462
Treatment of anhydrous YbCl3 with LiN(SiMe3)2 followed by reaction with 1 equivalent of 1,1,3,3,5,5‐hexaphenyl‐1,3,5‐trisiloxanediol afforded the first mono(trisiloxanediolate) complex of a rare earth element. The compound [Ph2Si(OSiPh2O)2]Yb(THF)(μ‐Cl)3Li2(THF)3 ( 1 ) was isolated in the form of colorless crystals in very high yield (93%). A single‐crystal X‐ray diffraction study confirmed the presence of an eight‐membered inorganic ring system containing ytterbium. Coordination of one THF ligand and retention of two equivalents of lithium chloride lead to formation of an “ate” complex. 相似文献
7.
Silicon‐ and Tin‐Containing Open‐Chain and Eight‐Membered‐Ring Compounds as Bicentric Lewis Acids toward Anions
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Dr. Anicet Siakam Wendji Dr. Christina Dietz Dr. Silke Kühn Michael Lutter Dr. Dieter Schollmeyer Dr. Wolf Hiller Prof. Dr. Klaus Jurkschat 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(1):404-416
Herein, we report the syntheses of silicon‐ and tin‐containing open‐chain and eight‐membered‐ring compounds Me2Si(CH2SnMe2X)2 ( 2 , X=Me; 3 , X=Cl; 4 , X=F), CH2(SnMe2CH2I)2 ( 7 ), CH2(SnMe2CH2Cl)2 ( 8 ), cyclo‐Me2Sn(CH2SnMe2CH2)2SiMe2 ( 6 ), cyclo‐(Me2SnCH2)4 ( 9 ), cyclo‐Me(2?n)XnSn(CH2SiMe2CH2)2SnXnMe(2?n) ( 5 , n=0; 10 , n = 1, X= Cl; 11 , n=1, X= F; 12 , n=2, X= Cl), and the chloride and fluoride complexes NEt4[cyclo‐ Me(Cl)Sn(CH2SiMe2CH2)2Sn(Cl)Me?F] ( 13 ), PPh4[cyclo‐Me(Cl)Sn(CH2SiMe2CH2)2Sn(Cl)Me?Cl] ( 14 ), NEt4[cyclo‐Me(F)Sn(CH2SiMe2CH2)2Sn(F)Me?F] ( 15 ), [NEt4]2[cyclo‐Cl2Sn(CH2SiMe2CH2)2SnCl2?2 Cl] ( 16 ), M[Me2Si(CH2Sn(Cl)Me2)2?Cl] ( 17 a , M=PPh4; 17 b , M=NEt4), NEt4[Me2Si(CH2Sn(Cl)Me2)2?F] ( 18 ), NEt4[Me2Si(CH2Sn(F)Me2)2?F] ( 19 ), and PPh4[Me2Si(CH2Sn(Cl)Me2)2?Br] ( 20 ). The compounds were characterised by electrospray mass‐spectrometric, IR and 1H, 13C, 19F, 29Si, and 119Sn NMR spectroscopic analysis, and, except for 15 and 18 , single‐crystal X‐ray diffraction studies. 相似文献
8.
Clifton L. Wagner Dr. Lizhi Tao Emily J. Thompson Dr. Troy A. Stich Dr. Jingdong Guo Dr. James C. Fettinger Prof. Louise A. Berben Prof. R. David Britt Prof. Shigeru Nagase Prof. Philip P. Power 《Angewandte Chemie (International ed. in English)》2016,55(35):10444-10447
The synthesis of the first linear coordinated CuII complex Cu{N(SiMe3)Dipp}2 ( 1 Dipp=C6H5‐2,6Pri2) and its CuI counterpart [Cu{N(SiMe3)Dipp}2]? ( 2 ) is described. The formation of 1 proceeds through a dispersion force‐driven disproportionation, and is the reaction product of a CuI halide and LiN(SiMe3)Dipp in a non‐donor solvent. The synthesis of 2 is accomplished by preventing the disproportionation into 1 by using the complexing agent 15‐crown‐5. EPR spectroscopy of 1 provides the first detailed study of a two‐coordinate transition‐metal complex indicating strong covalency in the Cu?N bonds. 相似文献
9.
Yan Wu Gui‐Ge Hou Jian‐Ping Ma Yu‐Bin Dong 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(6):m163-m165
The title molecular complex, [CoCl2(C22H18N6O)], features a novel 18‐membered Co‐containing metallocycle. The CoII atom lies in a fairly regular tetrahedral geometry defined by two imidazole N‐atom donors from one 2,5‐bis[3‐(1H‐1,3‐imidazol‐1‐ylmethyl)phenyl]‐1,3,4‐oxadiazole (L) ligand and two chloride anions. The coordinating orientation of the L ligand plays an important role in constructing the metallocycle complex. The complexes form a three‐dimensional supramolecular assembly via nonclassical C—H...Cl and C—H...N hydrogen bonds and π–π interactions. 相似文献
10.
The synthesis, characterization and ε‐caprolactone polymerization behavior of lanthanide amido complexes stabilized by ferrocene‐containing N‐aryloxo functionalized β‐ketoiminate ligand FcCOCH2C(Me)N(2‐HO‐5‐But‐C6H3) (LH2, Fc = ferrocenyl) are described. The lanthanide amido complexes [LLnN(SiMe3)2(THF)]2 [Ln = Nd ( 1 ), Sm ( 2 ), Yb ( 3 ), Y ( 4 )] were synthesized in good yields by the amine elimination reactions of LH2 with Ln[N(SiMe3)2]3(µ‐Cl)Li(THF)3 in a 1:1 molar ratio in THF. These complexes were characterized by IR spectroscopy and elemental analysis, and 1H NMR spectroscopy was added for the analysis of complex 4 . The definitive molecular structures of complexes 1 and 3 were determined by X‐ray diffraction studies. Complexes 1 – 4 can initiate the ring‐opening polymerization of ε‐caprolactone with moderate activity. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
11.
The structure of trans‐[Cr(Me2tn)2Cl2]2ZnCl4 (Me2tn = 2,2‐dimethylpropane‐1,3‐diamine) was determined by a single‐crystal X‐ray diffraction study at 173 K. The analysis reveals that there are three crystallographically independent chromium(III) complex cations in the title compound. The chromium(III) atoms are coordinated by four nitrogen atoms of Me2tn and two chlorine atoms in a trans arrangement, displaying a distorted octahedral geometry. The two six‐membered chelate rings in three complex cations are oriented in an anti chair–chair conformation with respect to each other. The Cr–N and Cr–Cl bond lengths average 2.0862(2) and 2.3112(6) Å, respectively. The ZnCl42– have slightly distorted tetrahedral arrangement with Zn–Cl lengths and the Cl–Zn–Cl angles are influenced by hydrogen bonding. The resolved absorption maxima in the electronic d–d spectrum were fitted with a secular determinant for a quartet energy state of the d3 configuration in a tetragonal field. It is confirmed that the nitrogen atoms of the Me2tn ligand are strong σ donors, but the chloro ligands have weak σ‐ and π donor properties toward the chromium(III) ion. 相似文献
12.
Lithium 8‐amidoquinoline ( 1 ) and lithium 8‐(trialkylsilylamido)quinoline [SiMe2tBu ( 2 ), SiiPr3 ( 3 )] react with dimethylgallium chloride to the metathesis products dimethylgallium 8‐amidoquinoline ( 4 ) as well as dimethylgallium 8‐(trialkylsilylamido)quinoline [SiMe2tBu ( 5 ), SiiPr3 ( 6 )]. The gallium atoms are in distorted tetrahedral environments. During the synthesis of 5 , orange dimethylgallium 2‐butyl‐8‐(tert‐butyldimethylsilylamido)quinoline ( 7 ) was found as by‐product. The metathesis reactions of Me2GaCl with LiN(R)CH2Py (Py = 2‐pyridyl) yield the corresponding 2‐pyridylmethylamides Me2Ga‐N(H)CH2Py ( 8 ), Me2Ga‐N(SiMe2tBu)CH2Py ( 9 ) and Me2Ga‐N(SiiPr3)CH2Py ( 10 ). In these complexes the gallium atoms show a distorted tetrahedral coordination sphere. However, derivative 8 crystallizes dimeric with bridging amido units whereas in 9 and 10 the 2‐pyridylmethylamido moieties act as bidentate ligands leading to monomeric molecules. 相似文献
13.
Ring‐opening polymerization of cyclic esters by pincer complexes derived from alkaline earth metals
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We report the synthesis and characterization of new Ca(II) and Mg(II) complexes of the type [Ph―PPP]MR (M = Ca, R = N(SiMe3)2 ( 1 ); M = Mg, R = nBu ( 2 )) where Ph―PPP? is a tridentate monoanionic ligand (Ph―PPP―H = bis(2‐diphenylphosphinophenyl)phosphine). Reaction of the opportune metal precursor (Ca[N(SiMe3)2]2.THF2 or MgnBu2) with 1 equiv. of the pro‐ligand Ph―PPP―H produces the corresponding calcium amido ( 1 ) or magnesium butyl ( 2 ) complex in high yield. Solution NMR studies show monomeric and kinetically stable structures for both species. The obtained complexes efficiently mediate the ring‐opening polymerization of ?‐caprolactone showing a turnover frequency of 40 000 h?1. In the presence of a hexogen alcohol, up to 2000 equiv. of monomer are converted by using a low loading of catalyst (5 µmol). Kinetic studies show a first‐order reaction in monomer concentration. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
14.
Dr. Erli Lu Josef T. Boronski Dr. Matthew Gregson Dr. Ashley J. Wooles Prof. Stephen T. Liddle 《Angewandte Chemie (International ed. in English)》2018,57(19):5506-5511
Unprecedented silyl‐phosphino‐carbene complexes of uranium(IV) are presented, where before all covalent actinide–carbon double bonds were stabilised by phosphorus(V) substituents or restricted to matrix isolation experiments. Conversion of [U(BIPMTMS)(Cl)(μ‐Cl)2Li(THF)2] ( 1 , BIPMTMS=C(PPh2NSiMe3)2) into [U(BIPMTMS)(Cl){CH(Ph)(SiMe3)}] ( 2 ), and addition of [Li{CH(SiMe3)(PPh2)}(THF)]/Me2NCH2CH2NMe2 (TMEDA) gave [U{C(SiMe3)(PPh2)}(BIPMTMS)(μ‐Cl)Li(TMEDA)(μ‐TMEDA)0.5]2 ( 3 ) by α‐hydrogen abstraction. Addition of 2,2,2‐cryptand or two equivalents of 4‐N,N‐dimethylaminopyridine (DMAP) to 3 gave [U{C(SiMe3)(PPh2)}(BIPMTMS)(Cl)][Li(2,2,2‐cryptand)] ( 4 ) or [U{C(SiMe3)(PPh2)}(BIPMTMS)(DMAP)2] ( 5 ). The characterisation data for 3 – 5 suggest that whilst there is evidence for 3‐centre P?C?U π‐bonding character, the U=C double bond component is dominant in each case. These U=C bonds are the closest to a true uranium alkylidene yet outside of matrix isolation experiments. 相似文献
15.
Mark Niemeyer 《无机化学与普通化学杂志》2002,628(3):647-657
The reaction of YbCl3 with two equivalents of NaN‐(SiMe3)2 has afforded a mixture of several ytterbium bis(trimethylsilyl) amides with the known complexes [Yb{N(SiMe3)2}2(μ‐Cl)(thf)]2 ( 1 ) and [Yb{N(SiMe3)2}3]( 4 ) as the main products and the cluster compound [Yb3Cl4O{N(SiMe3)2}3(thf)3]( 2 ) as a minor product. Treatment of 1 and 2 with hot n‐heptane gave the basefree complex [Yb{N(SiMe3)2}2(μ‐Cl)]2 ( 3 ) in small yield. The structures of compounds 1—4 and the related peroxo complex [Yb2{N(SiMe3)2}4(μ‐O2)(thf)2]( 5 ) have been investigated by single crystal X‐ray diffraction. In the solid‐state, 3 shows chlorobridged dimers with terminal amido ligands (av. Yb—Cl = 262.3 pm, av. Yb—N = 214.4 pm). Additional agostic interactions are observed from the ytterbium atoms to four methyl carbon atoms of the bis(trimethylsilyl)amido groups (Yb···C = 284—320 pm). DFT calculations have been performed on suitable model systems ([Yb2(NH2)4(μ‐Cl)2(OMe2)2]( 1m ), [Yb2(NH2)4(μ‐Cl)2]( 3m ), [Yb‐(NH2)3]( 4m ), [Yb2(NH24(μ‐O2)(OMe2)2]( 5m ), [Yb{N‐(SiMe3)2}2Cl] ( 3m/2 ) and Ln(NH2)2NHSiMe3 (Ln = Yb ( 6m ), Y ( 7m )) in order to rationalize the different experimentally observed Yb—N distances, to support the assignment of the O—O stretching vibration (775 cm ‐1) in the Raman spectrum of complex 5 and to examine the nature of the agostic‐type interactions in σ‐donorfree 3 . 相似文献
16.
2,4,6‐tris(4‐hydroxybenzimino)‐1,3,5‐triazine [ 1 , 2 ] ( III ) have been synthesized by the reaction of 1 equiv melamine and three equiv 4‐hydroxybenzaldehyde, and characterized by means of elemental analysis, 1H‐NMR (nuclear magnetic resonance spectroscopy), Fourier transform infrared (FTIR) spectrscopy, liquid chromatography‐mass spectroscopy (LC‐MS). L ( IV ) has been synthesized by the reaction of one equiv ( III ) and three equiv 4‐(thiophenoxy)phenyloxylohydroxymoyl chloride ( II ) , and characterized by means of the same methods. Then, four novel trinuclear Fe(III) and Cr(III) complexes involving tetradentate Schiff bases N,N′‐bis(salicylidene)ethylenediamine‐(salenH2) or bis(salicylidene)‐o‐phenylenediamine‐(salophen H2) with L (IV) have been synthesized and characterized by means of elemental analysis, FTIR spectrscopy, LC‐MS, thermal analyses. The metal ratios of the prepared complexes have been determined using AAS. The aim of the present study is synthesis of novel tridirectional‐trinuclear systems and to present their effects on magnetic behavior of [salenFe(III)], [salophenFe(III)], [salenCr(III)], and [salophenCr(III)] capped complexes. The complexes have also been characterized as low‐spin distorted octahedral Fe(III) and Cr(III) bridged by keton‐oxime group. J. Heterocyclic Chem., (2011). 相似文献
17.
Pierre Haquette Franck Lebideau Samuel Dagorne Jrme Marrot Grard Jaouen 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(11):m551-m552
The crystal structure of the title compound, chloro(η5‐cyclopentadienyl){(1R,2S)‐2‐[(diphenylphosphino)methylamino]‐1‐phenylpropyl diphenylphosphinite‐κ2P,P′}ruthenium(II), [Ru(C5H5)Cl(C34H33NOP2)], is reported. The pseudo‐octahedral complex is chiral and the configuration at the Ru atom is S. The seven‐membered metallacycle adopts a boat‐like conformation. 相似文献
18.
3‐Rhoda‐1,2‐diazacyclopentanes: A Series of Novel Metallacycle Complexes Derived From CN Functionalization of Ethylene
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Marcus W. Drover Daniel W. Beh Prof. Dr. Pierre Kennepohl Prof. Dr. Jennifer A. Love 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13345-13355
Rh‐containing metallacycles, [(TPA)RhIII(κ2‐(C,N)‐CH2CH2(NR)2‐]Cl; TPA=N,N,N,N‐tris(2‐pyridylmethyl)amine have been accessed through treatment of the RhI ethylene complex, [(TPA)Rh(η2‐CH2CH2)]Cl ([ 1 ]Cl) with substituted diazenes. We show this methodology to be tolerant of electron‐deficient azo compounds including azo diesters (RCO2N?NCO2R; R=Et [ 3 ]Cl, R=iPr [ 4 ]Cl, R=tBu [ 5 ]Cl, and R=Bn [ 6 ]Cl) and a cyclic azo diamide: 4‐phenyl‐1,2,4‐triazole‐3,5‐dione (PTAD), [ 7 ]Cl. The latter complex features two ortho‐fused ring systems and constitutes the first 3‐rhoda‐1,2‐diazabicyclo[3.3.0]octane. Preliminary evidence suggests that these complexes result from N–N coordination followed by insertion of ethylene into a [Rh]?N bond. In terms of reactivity, [ 3 ]Cl and [ 4 ]Cl successfully undergo ring‐opening using p‐toluenesulfonic acid, affording the Rh chlorides, [(TPA)RhIII(Cl)(κ1‐(C)‐CH2CH2(NCO2R)(NHCO2R)]OTs; [ 13 ]OTs and [ 14 ]OTs. Deprotection of [ 5 ]Cl using trifluoroacetic acid was also found to give an ethyl substituted, end‐on coordinated diazene [(TPA)RhIII(κ2‐(C,N)‐CH2CH2(NH)2‐]+ [ 16 ]Cl, a hitherto unreported motif. Treatment of [ 16 ]Cl with acetyl chloride resulted in the bisacetylated adduct [(TPA)RhIII(κ2‐(C,N)‐CH2CH2(NAc)2‐]+, [ 17 ]Cl. Treatment of [ 1 ]Cl with AcN?NAc did not give the Rh?N insertion product, but instead the N,O‐chelated complex [(TPA)RhI ( κ2‐(O,N)‐CH3(CO)(NH)(N?C(CH3)(OCH?CH2))]Cl [ 23 ]Cl, presumably through insertion of ethylene into a [Rh]?O bond. 相似文献
19.
Ingrid Bartz Joseph Grobe Kai Lütke‐Brochtrup Bernt Krebs Joachim Kuchinke Mechtild Lge 《无机化学与普通化学杂志》2001,627(6):1334-1346
Alternative Ligands. XXXVI. Novel Rhodium(I) Complexes with Donor/Acceptor Chelating Ligands In order to generate metal base/Lewis‐acid interactions in rhodium(I) phosphane complexes the binuclear complex [Rh(CO)2Cl]2 was reacted in benzene with dipod ligands of the type R2M′(OCH2PMe2)x(CH2CH2PMe2)2–x (R = F, Me; M′ = Si, Ge; x = 0–2) using the Ziegler dilution principle with the aim to produce mononuclear compounds in which with formation of five‐membered chelate rings in principle Rh → M′ contacts are possible. The reactions of ligands 1 – 7 (Table 1) with [Rh(CO)2Cl]2 proceed under CO elimination and, in spite of large turnovers, lead to a variety of products 8 – 14 (Table 1), in case of 11 , 13 and 14 accompanied by degradation of the corresponding ligands. Intact ligands are present in the 16‐membered rings of the binuclear complexes 8 – 10 and 12 , for which, due to the molecular structure, Rh → M′ interactions can be excluded. In the reaction of Me2Si(OCH2PMe2)2 ( 4 ) with [Rh(CO)2Cl]2 the unusual binuclear system 11 with a central Rh2O2 four‐membered ring and two RhO(SiMe2OCH2PMe2) six‐membered rings is formed. Small amounts of the mononuclear compounds Rh(CO)Cl(Me2PCH2OH)2 ( 13 ) and Rh(CO)Cl3(Me2PCH2OH)2 ( 14 ), respectively, are obtained in crystalline form from the reaction mixtures of [Rh(CO)2Cl]2 with Me2Ge(OCH2PMe2)(CH2CH2PMe2) ( 6 ) or Me2Ge(OCH2PMe2)2 ( 7 ). The new complexes were characterized by analytic (C, H), spectroscopic (NMR, IR, MS) and, except for 12 , by single crystal structural analyses. 相似文献
20.
Four‐Membered Heterometallacyclic d0 and d1 Complexes of Group 4 Metallocenes with Amidato Ligands
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Dr. Martin Haehnel Jacqueline B. Priebe Jacky C.‐H. Yim Dr. Anke Spannenberg Prof. Dr. Angelika Brückner Prof. Dr. Laurel L. Schafer Prof. Dr. Uwe Rosenthal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7752-7758
A study of the coordination chemistry of different amidato ligands [(R)N?C(Ph)O] (R=Ph, 2,6‐diisopropylphenyl (Dipp)) at Group 4 metallocenes is presented. The heterometallacyclic complexes [Cp2M(Cl){κ2‐N,O‐(R)N?C(Ph)O}] M=Zr, R=Dipp ( 1 a ), Ph ( 1 b ); M=Hf, R=Ph ( 2 )) were synthesized by reaction of [Cp2MCl2] with the corresponding deprotonated amides. Complex 1 a was also prepared by direct deprotonation of the amide with Schwartz reagent [Cp2Zr(H)Cl]. Salt metathesis reaction of [Cp2Zr(H)Cl] with deprotonated amide [(Dipp)N?C(Ph)O] gave the zirconocene hydrido complex [Cp2M(H){κ2‐N,O‐(Dipp)N?C(Ph)O}] ( 3 ). Reaction of 1 a with Mg did not result in the desired Zr(III) complex but in formation of Mg complex [(py)3Mg(Cl) {κ2‐N,O‐(Dipp)N?C(Ph)O}] ( 4 ; py=pyridine). The paramagnetic complexes [Cp′2Ti{κ2‐N,O‐(R)N?C(Ph)O}] (Cp′=Cp, R=Ph ( 7 a ); Cp′=Cp, R=Dipp ( 7 b ); Cp′=Cp*, R=Ph ( 8 )) were prepared by the reaction of the known titanocene alkyne complexes [Cp2′Ti(η2‐Me3SiC2SiMe3)] (Cp′=Cp ( 5 ), Cp′=Cp* ( 6 )) with the corresponding amides. Complexes 1 a , 2 , 3 , 4 , 7 a , 7 b , and 8 were characterized by X‐ray crystallography. The structure and bonding of complexes 7 a and 8 were also characterized by EPR spectroscopy. 相似文献