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1.
《Journal of organometallic chemistry》2010,695(24):2651-2657
Aminotin(II and IV) compounds {[(2,6-i-Pr-C6H3)(H)N]-μ-(Sn)-Cl}2, {2-[(CH3)2NCH2]C6H4}2Sn[N(H)(2,6-i-Pr-C6H3)]2 and {2-[(CH3)2NCH2]C6H4}Sn[N(2,6-i-Pr-C6H3)(SiMe3)] were prepared by lithium halide elimination from tin halides and corresponding lithium complexes. [(2,6-i-Pr-C6H3)(H)N]Li (1) reacts with one half of molar equivalent of SnCl2 to give {[(2,6-i-Pr-C6H3)(H)N]-μ-(Sn)-Cl}2. The same lithium amide (1) gave with R3SnCl corresponding aminostannanes. Further reactions of these compounds with n-butyllithium gave the starting 1 and tetraorganostannanes. {2-[(CH3)2NCH2]C6H4}2SnBr2 reacts with two equivalents of 1 to {2-[(CH3)2NCH2]C6H4}2Sn[N(H)(2,6-i-Pr-C6H3)]2. The dimeric heteroleptic stannylene {[(2,6-i-Pr-C6H3)(SiMe3)N](μ2-Cl)Sn}2 reacts with 2-[(CH3)2NCH2]C6H4Li to the monomeric {2-[(CH3)2NCH2]C6H4}Sn[N(2,6-i-Pr-C6H3)(SiMe3)]. The structure in the solid state and in solution and reactivity of products is also discussed. The unique decatin cluster has been isolated by hydrolysis of {[(2,6-i-Pr-C6H3)(H)N]-μ-(Sn)-Cl}2. The structure of some compounds was also evaluated by theoretical DFT methods. 相似文献
2.
Richard J. Bowen 《Journal of organometallic chemistry》2004,689(7):1230-1237
Treatment of (RH2C)2C5H3N-2,6 (R=SiMe3) with BunLi followed by addition of Me3SiCl gave the tetrasilyl pyridine derivative (R2HC)2C5H3N-2,6 1 in high yield. Further lithiation of 1 with BunLi and reaction of the intermediate with PhCN led to the new lithium-1-azaallyl [Li{N(R)C(Ph)C(R)(C5H3N-2,6)(CHR2)}]22, while metallation of the previously described di-lithium compounds [Li{N(R)C(R′)CH}2(C5H3-2,6)]Li(tmen)n (R=SiMe3, R′=But, n=1 or R=SiMe3, R′=Ph, n=2) with PdCl2(PhCN)2 yielded the novel metallacycles [Pd{{N(H)(R)C(R′)CH}{N(SiMe2CH2)C(R′)CH}C5H3N-2,6}] 3 (R′=But) and [Pd{{N(R)C(R′)CH}{N(R)(H)C(R′)CH}C5H3N-2,6}2] (R′=Ph) 4 in moderate to low yield. Compound 3 is unusual in being the first example of a crystallographically characterised PdNSiC heterocycle which is believed to be formed via an intramolecular CH-activation of a trimethylsilyl group by Pd(II). All four compounds were fully characterised by NMR-spectroscopy, microanalysis (not 4) and X-ray diffraction. 相似文献
3.
Sarish SP Nekoueishahraki B Jana A Roesky HW Schulz T Stalke D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(3):890-894
[L1AlMe]?THF ( 1 ; L1=CH[C(CH2)](CMe)(2,6‐iPr2C6H3N)2) is prepared by a new method to test its reactivity towards metal complexes to give heterobimetallic or polymetallic complexes. The treatment of 1 with germanium chloride ([LGeCl]), tin chloride ([LSnCl]; L=CH(CMe2,6‐iPr2C6H3N)2), bismuth amide ([1,8‐C10H6(NSiMe3)2BiNMe2]), and dimethyl zinc (ZnMe2) gave the desired compounds with different functional groups on the aluminum center. All compounds have been thoroughly characterized by multinuclear NMR spectroscopy, EI mass spectrometry, X‐ray crystallography ( 2 , 3 , and 5 ), and elemental analysis. 相似文献
4.
Herbert Schumann Jochen Gottfriedsen Sebastian Dechert Frank Girgsdies 《无机化学与普通化学杂志》2000,626(3):747-758
Homoleptic Amides of Zinc, Cadmium, and Mercury ZnCl2, CdCl2 and HgCl2 react with the lithium salts ( 1 a–5 a ) of the sterically demanding secundary amines HN(SiMe3)Ph ( 1 ), HN(SiMe3)C6H3Me2‐2,6 ( 2 ), HN(SiMe3)C6H3iPr2‐2,6 ( 3 ), HN(SiMe3)C6H3tBu2‐2,5 ( 4 ), and HN(SiMe2NMe2)C6H3iPr2‐2,6 ( 5 ) yielding the corresponding homoleptic metal amides Zn[N(SiMe2R′)R]2 ( 1 b–5 b ), Cd[N(SiMe2R′)R]2 ( 1 c , 5 c ), and Hg[N(SiMe2R′)R]2 ( 1 d–5 d ), respectively. Except the dimeric {Zn[N(SiMe3)Ph]2}2 ( 1 b ), all complexes are monomeric. The compounds were characterized by elemental analyses, molecular weight determinations, NMR and mass spectra. Furthermore, the zinc amides ( 1 b–5 b ) and the mercury amides 1 d–3 d and 5 d were characterized by single crystal X‐ray structure analysis. Except 1 b and 5 b , they show a linear N–M–N arrangement. 相似文献
5.
Yunjie Luo Yingming Yao Jinglei Chen Yong Zhang 《Journal of organometallic chemistry》2003,679(1):125-129
Reactions of [N(C6H3i-Pr2-2,6)(SiMe3)]2LnCl(THF) (Ln=Nd, Yb) with two equivalents of MeLi in a mixture solution of toluene and Et2O gave [N(C6H3i-Pr2-2,6)(SiMe3)]2LnCH3(μ-CH3)Li(THF)3·PhCH3 (Ln=Nd (1), Yb (2)) in good isolated yields as crystalline solids. The single-crystal structural analysis of 2 revealed that the coordination geometry of ytterbium ion is best described as a distorted pseudo-tetrahedron. Both 1 and 2 are active for the polymerization of methyl methacrylate to give syndiotactic-rich and high molecular weight polymers (Mn>104) with relatively narrow molecular weight distributions (Mw/Mn<2). 相似文献
6.
《Journal of organometallic chemistry》2007,692(1-3):536-544
The reaction of Ln(CH2SiMe3)3(thf)2 with 1 equiv. of the amine ligand 2,6-iPr2C6H3NH(SiMe3) gave the corresponding amido-ligated rare earth metal bis(alkyl) complexes [2,6-iPr2C6H3N(SiMe3)]Ln(CH2SiMe3)2(thf) (Ln = Sc (1), Y (2), Ho (3), Lu (4)), which represent rare examples of bis(alkyl) rare earth metal complexes bearing a monodentate anionic ancillary ligand. In the case of Gd, a similar reaction gave the bimetallic complex Gd2(μ-CH2SiMe2NC6H3iPr2-2,6)3(thf)3 (5) through intramolecular C–H activation of a methyl group of Me3Si on the amido ligand by Gd–CH2SiMe3 and the subsequent ligand redistribution. Complexes 1–5 were structurally characterized by X-ray analyses. On treatment with 1 equiv of [Ph3C][B(C6F5)4] in toluene at room temperature, complexes 1–4 showed high activity for the living polymerization of isoprene. The 1/[Ph3C][B(C6F5)4] system showed high activity also for the polymerization of 1-hexene and styrene. 相似文献
7.
V. Yu. Rad’kov A. V. Cherkasov T. A. Kovylina A. A. Trifonov 《Russian Chemical Bulletin》2016,65(12):2805-2811
A reaction of anhydrous yttrium chloride with an equimolar amount of lithium amidinateamidopyridinate obtained in situ by metallation of N,N’-bis(2,6-dimethylphenyl)-N-{6-[(2,6-dimethylphenyl)amino]pyridin-2-yl}acetimidamide ((2,6-Me2C6H3)NH(2,6-C6H3N)N(2,6-Me2C6H3)C(Me)=N(2,6-Me2C6H3), L1H) (1) with n-butyllithium in THF at–70 °C was used to synthesize the yttrium dichloride complex (L1)YCl2(THF)2 (2). The lutetium bis(alkyl) complex, namely, N’-(2,6-diisopropylphenyl)-N-(2,6-dimethylphenyl-N-{6-[(2,6-dimethylphenyl)amido]pyridin-2-yl}acetimidoamidinatebis(trimethylsilylmethyl)lutetium (4), was obtained by the reaction of N’-(2,6-diisopropylphenyl)-N-(2,6-dimethylphenyl)-N-(6-((2,6dimethylphenyl)amino)pyridin-2-yl)acetimidamide ((2,6-Me2C6H3)NH(2,6-C6H3N)N-(2,6-Me2C6H3)C(Me)=N(2,6-Pr 2 i C6H3), L2H (3)) with an equimolar amount of Lu(CH2SiMe3)3(THF)2. Complex 4 was found to be very stable and did not show indications of C—H-activation and other kinds of disintegration in benzene or toluene solution even upon prolonged heating at 60 °C. The reaction of complex 4 with an equimolar amount of 2,6-diisopropylaniline in toluene solution at room temperature led to the formation of the lutetium alkyl-anilide complex (L2)Lu(CH2SiMe3)(NH-2,6-Pr 2 i C6H3) (5). A three-component system 4—AlBu 3 i —[X][B(C6F5)4] ([X] = [Ph3C], [PhNHMe2], the molar ratio of 1: 10: 1) was found to catalyze polymerization of isoprene. 相似文献
8.
《Journal of organometallic chemistry》2007,692(1-3):217-224
The steric and electronic effects of bulky aryl and silyl groups on the Si–Si triple bonding in RSiSiR and the short Ga–Ga distance in Na2[RGaGaR] are investigated by density functional calculations. As typical bulky groups, Tbt = C6H2-2,4,6-{CH(SiMe3)2}3, Ar′ = C6H3-2,6-(C6H3-2,6-iPr2)2, Ar1 = C6H3-2,6-(C6H2-2,4,6-iPr3)2, SiMe(SitBu3)2, and SiiPrDis2 (Dis = CH(SiMe3)2) are investigated and characterized. The importance of large basis sets is emphasized for density functional calculations. 相似文献
9.
Philip P. Fontaine 《Journal of organometallic chemistry》2007,692(21):4683-4689
10.
New Aminometalanes of Aluminum and Gallium The reaction of secondary amines R′RNH with trimethyaluminum leads to the formation of dimeric aminoalanes [RR′NAlMe2]2 ( 1 ) (R = 2,6-Me2C6H3, R′ = SiMe2(2,4,6-Me3C6H2)) and 2 (R = Ph, R′ = SiMe3). Using a different stoichiometric ratio, a monomeric aminoalane [RR′N]2AlMe ( 3 ) (R = Ph, R′ = SiPh2Me) is obtained, having an aluminum atom of coordination number three due to the steric demand of the substituents. The synthesis of the corresponding aminogallanes 4 , 5 and 6 is achieved by reaction of lithium amides LiNRR′ (R = Ph, 2,6-iPr2C6H3; R′ = SiMe3, SiMe2iPr) with dimethylgalliumchloride, Me2GaCl, in n-hexane. The formation of the dimeric species is in 1 through carbon while that in 2 and 3 is formed through nitrogen. The X-ray single crystal structure analysis of 1 , 2 , 3 and 4 are reported. 相似文献
11.
Rafa? GrubbaAleksandra Wi?niewska Katarzyna BaranowskaEberhard Matern Jerzy Pikies 《Polyhedron》2011,30(7):1238-1243
Reactions of R2P-P(SiMe3)Li with [Cp2MCl2] (M = Zr, Hf) in hydrocarbons yield the related terminal phosphanylphosphido complexes [Cp2M(Cl){(Me3Si)P-PR2-κP1}] (R = iPr and tBu). The solid state structures of [Cp2M(Cl){P(SiMe3)-PiPr2-κP1}] (M = Zr, Hf) were established by single crystal X-ray diffraction studies. The phosphido-P atoms adopt almost planar geometries and the phosphanyl P atoms adopt pyramidal geometries. The reaction of a mixture of (Me3Si)2PLi and Ph2P-P(SiMe3)Li with [CpZrCl3] in toluene yields the dinuclear complex [Cp2Zr2Cl5(Ph2PPPSiMe3)(Li THF DME)]. 相似文献
12.
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
13.
Herbert Schumann Jrn Winterfeld Esther C. E. Rosenthal Holger Hemling Lothar Esser 《无机化学与普通化学杂志》1995,621(1):122-130
Organometallic Compounds of the Lanthanides. 88. Monomeric Lanthanide(III) Amides: Synthesis and X-Ray Crystal Structure of [Nd{N(C6H5)(SiMe3)}3(THF)], [Li(THF)2(μ-Cl)2Nd{N(C6H3Me2-2,6)(SiMe3)}2(THF)], and [ClNd{N(C6H3-iso-Pr2-2,6)(SiMe3)} 2(THF)] A series of lanthanide(III) amides [Ln{N(C6H5) · (SiMe3)}3(THF)x] [Ln = Y ( 1 ), La ( 2 ), Nd ( 3 ), Sm ( 4 ), Eu ( 5 ), Tb ( 6 ), Er ( 8 ), Yb ( 9 ), Lu ( 10 )] could be prepared by the reaction of lanthanide trichlorides, LnCl3, with LiN(C6H5)(SiMe3). Treatment of NdCl3(THF)2 and LuCl3(THF)3 with the lithium salts of the bulky amides [N(C6H3R2-2,6)(SiMe3)]? (R = Me, iso-Pr) results in the formation of the lanthanide diamides [Li(THF)2(μ-Cl)2Nd{N(C6H3Me2-2, 6)(SiMe3)}2(THF)] ( 11 ) and [ClLn{N(C6H3-iso-Pr2-2,6)(SiMe3)} 2(THF)] [Ln = Nd ( 12 ), Lu ( 13 )], respectively. The 1H- and 13C-NMR and mass spectra of the new compounds as well as the X-ray crystal structures of the neodymium derivatives 3 , 11 and 12 are discussed. 相似文献
14.
An alternative two-step synthesis of the previously reported bis(diphenylphosphinimino)methane [CH2(Ph2P = NC6H3iPr2-2,6)2] involving bromine oxidation of dppm and metathesis with 2,6-diisopropylaniline is described. [CH2(Ph2PNC6H3iPr2-2,6)2] is readily deprotonated by the transition metal silylamides [M{N(SiMe3)2}2] (M = Mn, Fe and Co) to provide a series of exclusively three-coordinate derivatives [{CH(Ph2PNC6H3iPr2-2,6)2M{N(SiMe3)2}] which have been characterised by elemental analysis, magnetic measurements and, in the case of the Fe derivative, X-ray structural analysis. Reactivity studies have shown that even such sterically demanding bis(phosphinimino)methanide ligands are prone to protonolysis and reductive [P(V) to P(III)] degradation which limits their utility as stable platforms for further M(II) derivitisation. 相似文献
15.
《Journal of Coordination Chemistry》2012,65(20):3718-3726
We report the synthesis and structural determination of three uranium(IV) complexes bearing two, four, and six salicylaldiminate ligands. Reaction of UI4(1,4-dioxane)2 with two, four, and six equivalents of K[OC6H4C(H)=N(2,6-iPr2C6H3)], 1, yielded [(2,6-iPr2C6H3)N=C(H)C6H4O-κ2(O,N)]2UI2(NCCH3), 2, [(2,6-iPr2C6H3)N=C(H)C6H4O-κ1(O)]2[(2,6-iPr2C6H3)N=C(H)C6H4O-κ2(O,N)]2U(THF), 3, and {[2,6-iPr2C6H3)N=C(H)C6H4O-κ1(O)]6U}2?, 4. While 2 shows normal κ2-coordination through both oxygen and nitrogen donors, 3 has two salicylaldiminate ligands bound only through oxygen and 4 has all six ligands bound only through oxygen. This is an exceedingly rare example of a chelating ligand not completing its chelation in f-element chemistry. In addition, 4 is the first report of a homoleptic octahedral actinide complex with a Schiff base ligand. 相似文献
16.
Sudhakar Padmanabhan Wei Wang Shohei Katao Kotohiro Nomura 《Macromolecular Symposia》2007,260(1):133-139
Syntheses of titanatranes containing [(O-2,4-Me2C6H2-6-CH2)2-{O(CH2)nCH2}]N3− (n = 1,2) have been explored. Catalytic activity for ethylene polymerization by Ti2(OiPr)2{[(O-2,4-Me2C6H2-6-CH2)2(µ2-OCH2-CH2)]N}2 ( 1a ) - MAO catalyst increased at high temperature; the activity also increased upon addition of AlMe3. Ti(O- 2,6-iPr2C6H3){[(O-2,4-Me2C6H2-6-CH2)2(OCH2CH2)]N} ( 1c ) showed higher activity than 1a under the same conditions. Ti{[(O-2,4-Me2C6H2-6-CH2)2(HOCH2CH2CH2)]N}2 was isolated from the reaction of Ti(OiPr)4 with bis(2-hydroxy-3,5-dimethylbenzyl)-propanolamine; the structure was determined by X-ray crystallography. 相似文献
17.
Elizabeth A. Jacobs Anna Fuller Simon J. Coles Graham J. Tizzard Joseph A. Wright Simon J. Lancaster 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(28):8647-8658
Treatment of Me2S ? B(C6F5)nH3?n (n=1 or 2) with ammonia yields the corresponding adducts. H3N ? B(C6F5)H2 dimerises in the solid state through N? H???H? B dihydrogen interactions. The adducts can be deprotonated to give lithium amidoboranes Li[NH2B(C6F5)nH3?n]. Reaction of the n=2 reagent with [Cp2ZrCl2] leads to disubstitution, but [Cp2Zr{NH2B(C6F5)2H}2] is in equilibrium with the product of β‐hydride elimination [Cp2Zr(H){NH2B(C6F5)2H}], which proves to be the major isolated solid. The analogous reaction with [Cp2HfCl2] gives a mixture of [Cp2Hf{NH2B(C6F5)2H}2] and the N? H activation product [Cp2Hf{NHB(C6F5)2H}]. [Cp2Zr{NH2B(C6F5)2H}2] ? PhMe and [Cp2Hf{NH2B(C6F5)2H}2] ? 4(thf) exhibit β‐B‐agostic chelate bonding of one of the two amidoborane ligands in the solid state. The agostic hydride is invariably coordinated to the outside of the metallocene wedge. Exceptionally, [Cp2Hf{NH2B(C6F5)2H}2] ? PhMe has a structure in which the two amidoborane ligands adopt an intermediate coordination mode, in which neither is definitively agostic. [Cp2Hf{NHB(C6F5)2H}] has a formally dianionic imidoborane ligand chelating through an agostic interaction, but the bond‐length distribution suggests a contribution from a zwitterionic amidoborane resonance structure. Treatment of the zwitterions [Cp2MMe(μ‐Me)B(C6F5)3] (M=Zr, Hf) with Li[NH2B(C6F5)nH3?n] (n=2) results in [Cp2MMe{NH2B(C6F5)2H}] complexes, for which the spectroscopic data, particularly 1J(B,H), again suggest β‐B‐agostic interactions. The reactions proceed similarly for the structurally encumbered [Cp′′2ZrMe(μ‐Me)B(C6F5)3] precursor (Cp′′=1,3‐C5H3(SiMe3)2, n=1 or 2) to give [Cp′′2ZrMe{NH2B(C6F5)nH3?n}], both of which have been structurally characterised and show chelating, agostic amidoborane coordination. In contrast, the analogous hafnium chemistry leads to the recovery of [Cp′′2HfMe2] and the formation of Li[HB(C6F5)3] through hydride abstraction. 相似文献
18.
Andreas Stasch Sankaranarayana Pillai Sarish HerbertW. Roesky Kathrin Meindl Fabio Dall'Antonia Thomas Schulz Dietmar Stalke 《化学:亚洲杂志》2009,4(9):1451-1457
The synthesis of N‐heterocyclic carbene adducts of alkynyl lithium and magnesium is achieved, and different degrees of association are observed. Reaction of strontium amide nacnacSrN(SiMe3)2(thf) (nacnac=CH(CMe2,6‐iPr2C6H3N)2) with PhC≡CH in THF yields the dimeric alkynyl complex [nacnacSr(thf)(μ‐C≡CPh)]2 which shows an interesting coordination geometry around the metal center. The compound retains the THF molecules, unlike its lighter congener, even in hydrocarbon solvents. 相似文献
19.
Robert E. Mulvey Alan R. Kennedy J. Hilko Schulte 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(11):1288-1289
The metallation reaction between dibutylmagnesium and 2,6-diisopropyl-N-(trimethylsilyl)aniline gives the unusual monomeric three-coordinate complex (diethyl ether-κO)bis[2,6-diisopropyl-N-(trimethylsilyl)anilido-κN]magnesium(II), [Mg(C15H26NSi)2(C4H10O)] or [Mg{(Me3Si)(2,6-iPr2C6H3)N}2(Et2O)]. This low-coordinate species has a distorted trigonal-planar coordination environment, with an additional short Mg—Cipso contact of 2.799 (2) Å. 相似文献
20.
Homo- and heteroleptic N-arylsalicylaldiminate derivatives of TiIV and ZrIV of the type, MX4–x
(OC6H4CH=NAr)
x
(X = OPri, x = 2,3; X = Cl, x = 1,2,3,4; Ar = C6H3Me2-2,6, C6H3Et2-2,6) have been prepared by reactions in the desired molar ratios of: (i) Ti(OPri)4/Zr(OPri)4·PriOH with N-arylsalicylaldimines in benzene, and (ii) MCl4 (M = Ti, Zr) with Me3SiOC6H4CH=NAr or HOC6H4CH=NAr in the presence of Et3N as a base or the potassium salt of N-arylsalicylaldimines in benzene. The three homoleptic derivatives of CrIII, Cr(OC6H4CH=NAr)3 (Ar = C6H2Me3-2,4,6, C6H3Et2-2,6, C6H3Pri
2-2,6) have also been prepared by salt-elimination. All of these new derivatives have been characterized by elemental analyses, spectroscopic [i.r., 1H and 13C-n.m.r. (Ti and Zr complexes), and electronic (for Cr complexes)] studies, as well as molecular weight measurements. 相似文献