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1.
Richard J. Bowen Manuel A. Fernandes Patricia W. Gitari Marcus Layh 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6):1403-1418
Alkytris(2-pyridyl)phosphonium salts [(2-Py) 3 PR]X 1 [1a, R = Et, X = Br; 1b, R = Pr, X = Br; 1c, R = Bu, X = Br; 1d, R = CH2Ph, X = Br; 1e, R = CH 2 Ph, X = Cl] were synthesised from (2-Py) 3 P and an excess of RCl. 1c and 1e were found to rapidly decompose in hot acetone to 2,2′-bipyridinium(+1) bromide 2 and (2-Py)P(O)(CH 2 Ph)C(OH)Me 2 3, respectively. A reaction mechanism for both products is proposed. All compounds were fully characterized, including X-ray crystallography for 1a and 3 with 1a being the first representative of this class of compounds characterized by this technique. 相似文献
2.
Jacek E. Nycz 《Phosphorus, sulfur, and silicon and the related elements》2013,188(10):2605-2612
The present study shows new aspects of the synthesis of polyhalogenoarylphosphanes. The sterically hindered anions Ph(R)P-Y? (1a–c, Y = O, lone pair; R = Ph, But) have been used to show the complexity of the reaction between phosphorus nucleophiles and hexahalogenobenzenes or 9-bromofluorene (E3). The Ph(But)P-O? (1a) anion reacts with hexachlorobenzene (E1), hexafluorobenzene (E2), or E3 to give Ph(R)P(O)X (4a–c, X = F, Cl, Br) with the release of the corresponding carbanion as a nucleofuge, followed by side reactions. In contrast, the lithium phosphides Ph(R)PLi (1b,c) react with hexahalogenobenzenes to give the corresponding diphosphanes 5a,b as the main product and traces of P-arylated products, i.e., Ph(R)P-C6X5 (10a,b, X = Cl, F). Unexpectedly, Ph(But)PLi (1b) reacts with an excess of 9-bromofluorene to give only halogenophosphane Ph(But)P-X. 相似文献
3.
Kai Li Hongjian Sun Wenjing Yang Yajie Wang Shangqing Xie Xiaoyan Li Olaf Fuhr Dieter Fenske 《应用有机金属化学》2020,34(3):e5337
A series of phosphorus-chalcogen chelated hydrido iron (II) complexes 1–7 , (o-(R'2P)-p-R-C6H4Y)FeH (PMe3)3 ( 1 : R = H, R' = Ph, Y = O; 2 : R = Me, R' = Ph, Y = O; 3 : R = H, R' = iPr, Y = O; 4 : R = Me, R' = iPr, Y = O; 5 : R = H, R' = Ph, Y = S; 6 : R = Me, R' = Ph, Y = S; 7 : R = H, R' = Ph, Y = Se), were synthesized. The catalytic performances of 1–7 for dehydration of amides to nitriles were explored by comparing three factors: (1) different chalcogen coordination atoms Y; (2) R' group of the phosphine moiety; (3) R substituent group at the phenyl ring. It is confirmed that 5 with S as coordination atom has the best catalytic activity and 7 with Se as coordination atom has the poorest catalytic activity among complexes 1 , 5 and 7 . Electron-rich complex 4 is the best catalyst among the seven complexes and the dehydration reaction was completed by using 2 mol% catalyst loading at 60 °C with 24 hr in the presence of (EtO)3SiH in THF. Catalyst 4 has good tolerance to many functional groups. Among the seven iron complexes, new complexes 3 and 4 were obtained via the O-H bond activation of the preligands o-iPr2P(C6H4)OH and o-iPr2P-p-Me-(C6H4)OH by Fe(PMe3)4. Both 3 and 4 were characterized by spectroscopic methods and X-ray diffraction analysis. The catalytic mechanism was experimentally studied and also proposed. 相似文献
4.
Navabeeh Nami Chamazi Majid M. Heravi Thees Breyhan Bernhard Neumüller Prof. Dr. 《无机化学与普通化学杂志》2007,633(8):1243-1245
Reaction of (R,R)‐(N,N′)‐Diisopropylcyclohexyl‐1,2‐diamine with Me2MCl (M = Ga, In) (R,R)‐(N,N′)‐Diisopropylcyclohexyl‐1,2‐diamine (H2L) was reacted with Me2GaCl and Me2InCl in boiling toluene, respectively. In both cases the salt [Me2M(H2L)][Me2MCl2] [M = Ga ( 1 ), In ( 2 )] was formed. 1 and 2 were characterized by NMR and vibrational spectroscopy. In addition, an X‐ray structure determination was applied on 2 . According to the spectroscopical and structural findings 1 and 2 consist of cations [Me2M(H2L)]+ and anions [Me2MCl2]?. 相似文献
5.
The complexes Mo{HB(Me2pyz)3}(NO)XY {HB(Me2pyz)3 HB(3, 5-Me2C3HN2)3; X=Y=F, Cl or Br; X=F, Y=OEt, NHMe or SBun; X=Cl, Y=NHR (R=Me Et, Bun, Ph, p-MeC6H4), NMe2 and SR (R=Bun, C6H11, CH2Ph, Ph); X=Br, Y=NHMe, NMe2 and SBun} have been prepared and characterised spectroscopically. Their properties are generally similar to those of their iodo-analogues. 相似文献
6.
Wilfredo Hernndez Evgenia Spodine Rainer Richter Karl‐Heinz Hallmeier Uwe Schrder Lothar Beyer 《无机化学与普通化学杂志》2003,629(14):2559-2565
The platinum(II) mixed ligand complexes [PtCl(L1‐6)(dmso)] with six differently substituted thiourea derivatives HL, R2NC(S)NHC(O)R′ (R = Et, R′ = p‐O2N‐Ph: HL1; R = Ph, R′ = p‐O2N‐Ph: HL2; R = R′ = Ph: HL3; R = Et, R′ = o‐Cl‐Ph: HL4; R2N = EtOC(O)N(CH2CH2)2N, R′ = Ph: HL5) and Et2NC(S)N=CNH‐1‐Naph (HL6), as well as the bis(benzoylthioureato‐κO, κS)‐platinum(II) complexes [Pt(L1, 2)2] have been synthesized and characterized by elemental analysis, IR, FAB(+)‐MS, 1H‐NMR, 13C‐NMR, as well as X‐ray structure analysis ([PtCl(L1)(dmso)] and [PtCl(L3, 4)(dmso)]) and ESCA ([PtCl(L1, 2)(dmso)] and [Pt(L1, 2)2]). The mixed ligand complexes [PtCl(L)(dmso)] have a nearly square‐planar coordination at the platinum atoms. After deprotonation, the thiourea derivatives coordinate bidentately via O and S, DMSO bonds monodentately to the PtII atom via S atom in a cis arrangement with respect to the thiocarbonyl sulphur atom. The Pt—S‐bonds to the DMSO are significant shorter than those to the thiocarbonyl‐S atom. In comparison with the unsubstituted case, electron withdrawing substituents at the phenyl group of the benzoyl moiety of the thioureate (p‐NO2, o‐Cl) cause a significant elongation of the Pt—S(dmso)‐bond trans arranged to the benzoyl‐O—Pt‐bond. The ESCA data confirm the found coordination and bonding conditions. The Pt 4f7/2 electron binding energies of the complexes [PtCl(L1, 2)(dmso)] are higher than those of the bis(benzoylthioureato)‐complexes [Pt(L1, 2)2]. This may indicate a withdrawal of electron density from platinum(II) caused by the DMSO ligands. 相似文献
7.
α‐Diimine ligands react with the platinum(II) alkyl complexes [(Me2S)PtMe2]2 and (Me2S)2PtClMe to form (RDABR′)PtMe2 and (RDABR′)PtClMe (RDABR′=RN=CR′−CR′=NR; R=2,6‐Me2Ph, 2,6‐(CHMe2)2Ph, 3,5‐Me2Ph, 3,5‐(CF3)2Ph, C6H11; R′=Me, H). The oxidation of these complexes with Cl2, I2, N‐chlorosuccinimide, [PtCl6]2− and (TMEDA)PtMe2I2 has been investigated. Attempts to determine the oxidation potentials of the PtII complexes electrochemically yielded only irreversible one‐electron oxidations. However, a qualitative ordering of increasing difficulty of oxidation has been determined for the series (RDABR′)PtMe2<(RDABR′)PtClMe<(RDABR′)PtCl2≪(RDABR′)PtMe(solvent)]+. The oxidation proceeds via a two‐electron inner‐sphere electron transfer from a bridged binuclear intermediate. The oxidation of (RDABR′)PtMe2 by (TMEDA)PtMe2I2 exhibits characteristic third‐order kinetics, first‐order each in [PtII], [PtIV] and [I−]. Oxidation by a one‐electron process in MeCN solution results in a rapid subsequent disproportionation to PtIIMe and PtIVMe3 cations with MeCN occupying the fourth or sixth coordination sites. Single‐crystal X‐ray structure determinations for [(2,6‐Me2PhDABMe)PtMe3(MeCN)]+[PtCl6]0.5(MeCN) and [(CyDABH)PtMe3(MeCN)]+[PtCl6]0.5(MeCN) are reported. 相似文献
8.
Herbert Schumann Jens Kaufmann Birgit C. Wassermann Frank Girgsdies Nimer Jaber Jochanan Blum 《无机化学与普通化学杂志》2002,628(5):971-978
The enantiomerically pure dimeric N, O‐5‐chelates [Me2In(μ‐OCH2CH(R)NMe2)]2 {R = Me (S) ( 2 ); R = iPr (S) ( 3 ); R = iBu (S) ( 4 ); R = Bz (S) ( 5 )}, and [Me2In‐{μ‐(1R, 2S)‐OCH(Ph)CH(Me)NMe2}]2 ( 6 ), as well as the achiral dimeric N, O‐6‐chelate [Me2In(μ‐O(CH2)3NMe2)]2 ( 7 ) have been synthesized from trimethylindium and equimolar amounts of the corresponding enantiomerically pure dimethylamino alcohols or of the achiral dimethylaminopropanol by elimination of methane. Their 1H NMR, 13C NMR, and mass spectra as well as the X‐ray single crystal structure analyses of [Me2In{μ‐O(CH2)2NMe2}]2 ( 1 ), 3, 5, 6 and 7 are described and discussed. The coordinative N→In bonds of the five‐coordinate indium complexes show dynamic dissociation/association processes. 1—6 were found to be useful reagents for the partial kinetic resolution of 2‐carbomethoxy‐1, 1′‐binaphthyl triflate. 相似文献
9.
Georg Grötsch Wolfgang Malisch Herbert Blau 《Journal of organometallic chemistry》1983,252(2):C19-C22
The reaction of the phosphonium metallates Me4P[C5R5(CO)(Me3P))R′] (M = W, R = H, R′ = Et (1a); M = Mo, R = Me, R′ = Me (1b)) with the silylating reagent Me3SiOSO2CF3 yields the neutral complexes C5R5(CO)(Me3P))R (2a, 2b) bearing a chelating O(2), C(4)-trimethylsiloxybutenone ligand. The structure of the new compounds is established by the IR, 1H and 31P NMR spectra. 相似文献
10.
《Comptes Rendus Chimie》2003,6(2):209-222
The synthesis of the iron allenylidene complexes [(η5-C5Me5)(η2-dppe)Fe(=C=C=C(Ph)Ph)][X] (5a, X = PF6, 95%; 5b, X = BPh4, 91%; dppe = 1,2-bis(diphenylphosphino)ethane) was achieved by reacting the complex (η5-C5Me5)(η2-dppe)FeCl (10) with 1 equiv of 1,1-diphenyl-prop-2-yn-1-ol in methanol in the presence of KPF6 or NaBPh4. Surprisingly, when the reaction was carried out in the presence of the tetraphenylborate anion, the final product contained both 5b and the hydroxyvinylidene [(η5-C5Me5)(η2-dppe)Fe(=C=C(H)C(OH)(Ph)2)][BPh4] (14b) in the 1:1 ratio. Further treatment of the mixture with Amberlyst 15 in methanol provided the allenylidene 5b as a pure sample. The allenylidene complexes [(η5-C5Me5)(η2-dppe)Fe(=C=C=C(Me)Ph)][PF6] (6) and [(η5-C5Me5)(η2-dppe)Fe(=C=C=C(Me)Et)][PF6] (7) were prepared according to the same procedure and they were isolated as purple powders in 90% yield. The X-ray crystal structures were determined for the vinylidene complexes [(η5-C5Me5)(η2-dppe)Fe(=C=CH2)][PF6] (3) and [(η5-C5Me5)(η2-dppe)Fe(=C=C(Ph)H)][PF6] (4), and the allenylidene derivative 5a. In the homogeneous series of complexes [(η5-C5Me5)(η2-dppe)Fe(=(C)n(R)R’)][PF6], (n = 1, R = H, R′ = Me, X = PF6, 1; n =1, R = H, R’ = OMe, X = PF6, 2a; n = 1, R = H, R’ = OMe, X = CF3OSO2, 2b; n = 2, R = R′ = H, X = PF6, 3; n = 2, R = H, R′ = Ph, X = PF6, 4; n = 3, R = R′ = Ph, X = PF6, 5a; n = 3, R = R′ = Ph, X = BPh4, 5b; n = 3, R = Me, R′ = Ph, X = PF6, 6; n = 3, R = Me, R′ = Et, X = PF6, 7; n = 3, R = Me, R′ = OMe, X = BPh4, 8), an empiric relationship between the Mössbauer parameters, δ and QS, was found. This observation would indicate that the positive charge on the iron nucleus decreases with the Fe=C bond order. Moreover, in this series of iron cumulenylidene derivatives, comparison of the variation of the metal–carbon bond distances determined by X-ray analyses with the Mössbauer QS values allows the observation of a linear correlation (R = 0.99). To cite this article: G. Argouarch et al., C. R. Chimie 6 (2003). 相似文献
11.
《Journal of Coordination Chemistry》2012,65(10):1622-1634
Reactions of Al(OPri)3 with LH2 =?[R′C(NYOH)CHC(R)OH] R=R′=CH3, Y =?(CH2)2 (L1H2); R =?CH3, R′ =?C6H5, Y =?(CH2)2 (L2H2); R =?R′ =?CH3, Y =?(CH2)3 (L3H2); R =?CH3, R′ =?C6H5, Y =?(CH2)3 (L4H2), in 1 : 2 molar ratio give mononuclear derivatives of aluminium AlLLH (1a–1d). Equimolar reactions of AlLLH with M(OPri)3 (M =?Al and B) yield homo- and hetero-dinuclear derivatives AlLLM(OPri)2 (M=Al=2a–2d M=B=3a–3d). Reaction of 2a with L1H2 affords AlL1L1AlL1 (4). All these derivatives have been characterized by elemental analysis, molecular weight measurements and plausible structures have been suggested on the basis of IR, NMR [1H, 13C, 27Al and 11B] spectral data and FAB-mass studies of 2b and 3b. Schiff base L1H2 and its mononuclear derivative with aluminium (AlL1L1H) have been screened for their antibacterial activity against Escherischia coli and Bacillus subtilis. 相似文献
12.
Timothy R. Totsch Victoria L. Stanford Oleksander Klep Mary K. Burdette Benjamin Grant Stephen H. Foulger Gary M. Gray 《Journal of polymer science. Part A, Polymer chemistry》2020,58(13):1825-1842
Linear polyphosphonates with the generic formula –[P(Ph)(X)OR′O]n– (X = S or Se) have been synthesized by polycondensations of P(Ph)(NEt2)2 and a diol (HOR′OH = 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, tetraethylene glycol, or 1,12-dodecanediol) followed by reaction with a chalcogen. Random copolymers have been synthesized by polycondensations of P(Ph)(NEt2)2 and mixture of two of the diols in a 2:1:1 mol ratio followed by reaction with a chalcogen. Block copolymers with the generic formula –[P(Ph)(X)OR′O](x + 2) –[P(Ph)(X)OR′O](x + 3)– (X = S or Se) have been synthesized by the polycondensations of Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2 oligomers with HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers followed by reaction with a chalcogen. The Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2 oligomers are prepared by the reaction of an excess of P(Ph)(NEt2)2 with a diol while the HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers are prepared by the reaction of P(Ph)(NEt2)2 with an excess of the diol. In each case the excess, x is the same and determines the average block sizes. All of the polymers were characterized using 1H, 13C{1H}, and 31P{1H} NMR spectroscopy, TGA, DSC, and SEC. 31P{1H} NMR spectroscopy demonstrates that the random and block copolymers have the expected arrangements of monomers and, in the case of block copolymers, verifies the block sizes. All polymers are thermally stable up to ~300°C, and the arrangements of monomers in the copolymers (block vs. random) affect their degradation temperatures and Tg profiles. The polymers have weight average MWs of up to 3.8 × 104 Da. 相似文献
13.
A Dimeric Gallium Hydrazide as an Active Lewis Pair – Complexation and Activation of Me2GaH and Various Heterocumulenes
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Werner Uhl Matthias Willeke Alexander Hepp Damian Pleschka Marcus Layh 《无机化学与普通化学杂志》2017,643(5):387-397
Treatment of the dimeric gallium hydrazide [Me2Ga‐N(2‐Ad)‐NC5H10]2 ( 5 ) with Me2GaH resulted in the formation of an adduct 6 by Ga–N bond cleavage and coordination of the metal hydride via a Ga–N and a 3c–2e Ga–H–Ga bond. This reaction reflects the typical behavior of frustrated Lewis pairs. Reactions with heterocumulenes R–N=C=X (R = Ph, CMe3, Dipp, X = O; R = Ph, X = S) or X=C=X (X = O, S) resulted in the formation of the cyclic Ga–N insertion products Me2Ga–N(R)C(O)N(2‐Ad)‐NC5H10 ( 7a – c ), Me2GaS2C‐N(2‐Ad)‐NC5H10 ( 8 ) or Me2GaX2C‐N(2‐Ad)‐NC5H10 [X = O ( 9 ); S ( 10 )] in moderate to good yields. Three different structural motifs were observed in the solid state: Five‐membered GaNCN2 heterocycles with exocyclic C=O bonds for compounds 7a – c , four‐membered GaSCN or GaSCS heterocycles for compounds 8 and 9 (chelating coordination of the Ga atoms by SCN and CS2 ligands) and an eight‐membered (GaOCO)2 heterocycle for the dimeric CO2 insertion product 10 . Treatment of 5 with PhCN or Ph2CO resulted in a completely different reaction and afforded a dimeric Ga imide 11a or an alcoholate 11b . These reactions may start by retro‐hydrogallation with the formation of H10C5N–N=C(C9H14) and Me2GaH and proceed by addition of the metal hydride to the polar multiple bonds of the nitrile or ketone. 相似文献
14.
Two modes of reactivity of N-silylphosphoranimines have been utilized to prepare the title compounds containing either B–N=P or Si–N=P–N–B linkages. First, silicon-nitrogen bond cleavage reactions of the N-silylphosphoranimines, Me3SiN=PMe(R)OCH2CF3 (1: R=Me, 2: R=Ph), with various chloroboranes gave the new N-borylphosphoranimines, Ph(Me2N)B–N=PMe2OCH2CF3 (2) and [(Me3Si)2N](Cl)B–N=PMe2OCH2CF3 (10). In other cases, however, the expected B–N=P products were unstable and cyclic phosphazenes [Me(R)P=N]3,4 were obtained. Second, deprotonation-substitution reactions of the aminophosphoranimines, Me3SiN=P(R)Me–N(R)H, were used to prepare a series of novel (borylamino)-phosphoranimines, Me3SiN=P(R)(Me)–N(R)–B(NMe2)2 (18: R=Me, R=t-Bu; 19: R=R=Me; 20: R=Ph, R=t-Bu; 21: R=Ph, R=Me) and Me3SiN=PMe2–N(t-Bu)–B(Ph)X (22: X=NMe2, 23: X=OCH2CF3). All of the new boron–nitrogen–phosphorus products were fully characterized by multinuclear NMR (1H, 13C, and 31P) spectroscopy and elemental analysis. 相似文献
15.
Monomeric Dialkyl Metal Complexes of the R2M(NR′)2XR Type with M = Al, Ga, In, Tl; X = S, C and R, R′ = Alkyl and Silyl N,N′-Bis(trimethylsilyl)sulfurdiimide reacts with the trimethyl derivatives of aluminium, gallium, and indium within insertion. Hereby monomeric sulfinic acid imidamidates Me2M(NSiMe3)2SMe (Me = CH3) are formed. The lithium amidinates Li(NR′)2CMe (R′ = i-C3H7 and SiMe3) are formed likewise by insertion reactions with LiMe and the corresponding carbodiimides R′N?C?NR′ and were used in reactions with R2MCl (M = Al to Tl) to synthesize dialkyl metal amidinates R2M(NR′)2CMe. The NMR (1H and 13C) and the vibrational spectra (IR and Raman) are discussed and applied to describe the structure of these chelat complexes. 相似文献
16.
Werner Uhl Frank Hengesbach Jennifer Isermann Meisam Soleimani Lina Schürmann Alexander Hepp Marcus Layh 《无机化学与普通化学杂志》2019,645(20):1205-1214
Hydrogallation of Me3Si–C≡C–NR'2 with R2Ga–H (R = tBu, CH2tBu, iBu) yielded Ga/N‐based active Lewis pairs, R2Ga–C(SiMe3)=C(H)–NR'2 ( 7 ). The Ga and N atoms adopt cis‐positions at the C=C bonds and show weak Ga–N interactions. tBu2GaH and Me3Si–C≡C–N(C2H4)2NMe afforded under exposure of daylight the trifunctional digallium(II) compound [MeN(C2H4)2N](H)C=C(SiMe3)Ga(tBu)–Ga(tBu)C(SiMe3)=C(H)[N(C2H4)2NMe] ( 8 ), which results from elimination of isobutene and H2 and Ga–Ga bond formation. 8 was selectively obtained from the ynamine and [tBu(H)Ga–Ga(H)tBu]2[HGatBu2]2. 7a (R = tBu; NR'2 = 2,6‐Me2NC5H8) and H8C4N–C≡N afforded the adduct tBu2Ga‐C(SiMe3)=C(H)(2,6‐Me2NC5H8) · N≡C–NC4H8 ( 11 ) with the nitrile bound to gallium. The analogous ALP with harder Al atoms yielded an adduct of the nitrile dimer or oligomers of the nitrile at room temperature. The reaction of 7a with Ph–N=C=O led to the insertion of two NCO groups into the Ga–Cvinyl bond to yield a GaOCNCN heterocycle with Ga bound to O and N atoms ( 12 ). 相似文献
17.
Dr. Qing You Prof. Dr. Jie Zhang Prof. Dr. Xigeng Zhou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(34):7702-7710
A new method for the modification of a silylamino ligand has been developed through mono and dual C(sp3)−H/Si−H cross-dehydrocoupling with silanes. The reaction of [LY{η2-(C,N)-CH2Si(Me2)NSiMe3}] (L=bis(2,6-diisopropylphenyl)-β-diketiminato, L′ ( 1L ′); L=tris(3,5-dimethylpyrazolyl)borate, TpMe2 ( 1TpMe2 )) with 2 equivalents of PhSiH3 in toluene gave the complexes [LY{η2-(C,N)-C(SiH2Ph)2Si(Me2)NSiMe3}] (L=L′ ( 2L’ ); L=TpMe2 ( 2TpMe2 )). Moreover, 1TpMe2 reacted with the secondary silanes Ph2SiH2 and Et2SiH2 to afford the corresponding mono C−H activation products [TpMe2Y{η2-(C,N)-CH(SiHR2)Si(Me2)NSiMe3}] (R=Ph ( 4 b ); R=Et ( 4 c )). The equimolar reaction of 1TpMe2 with PhSiH3 also produced the mono C−H activation product 4 a ([TpMe2Y{η2-(C,N)-CH(SiH2Ph)Si(Me2)NSiMe3}(thf)]). A study of their reactivity showed that 4 a facilely reacted with 2 equivalents of benzothiazole by an unusual 1,1-addition of the C=N bond of the benzothiazolyl unit to the Si−H bond to give the C−H/Si−H cross-dehydrocoupling product [(TpMe2)Y{η3-(N,N,N)-N(SiMe3)SiMe2CH2Si(Ph)(CSC6H4N)(CHSC6H4N)}] ( 5 ). These results indicate that this modification endows the silylamino ligand with novel reactivity. 相似文献
18.
Synthesis and Structure of C,N‐difunctionalized Sulfinimideamides Sulfurdiimides RN=S=NR ( 1 a , b ) react in diethyl ether with two equivalents of lithiummethyl to give dimeric C,N‐dilithiummethylenesulfinimideamide ether adducts {Li2[H2C–S(NR)2 · Et2O]}2 ( 2 a , b ) ( a : R = tBu, b : R = SiMe3). Metathesis of 2 b with four equivalents of Me3SiCl, Me3SnCl or Ph3SnCl yields the corresponding C,N‐bis‐substituted sulfinimideamides R3EH2C–S[N(SiMe3)2]NER3 ( 3 – 5 ) ( 3 : R = Me, E = Sn; 4 : R = Ph, E = Sn; 5 : R = Me, E = Si). The crystal structures of 2 a and 2 b were determined by X‐ray structure analysis. Both compounds form centrosymmetric cage structures consisting of two distorted face sharing cubes ( 2 a : space group P1 (No. 2); Z = 2 (4 · 0,5); 2 b : space group C2/c (No. 15), Z = 4). 相似文献
19.
Kanupriya Sharma Nandu Bala Sharma Anirudh Singh 《Phosphorus, sulfur, and silicon and the related elements》2013,188(12):2735-2744
Equimolar reactions of BuSn(OPri)3 with diethanolamines, RN(CH2CH2 OH) 2 (abbreviated as RdeaH2, where R = H or Me), afford dimeric isopropoxo-bridged six-coordinate butyltin(IV) complexes [{Bu(η3-Rdea)Sn(μ-OPri)}2] (R = H ( 1 ), Me ( 2 )). Interactions between BuSn(OPri)3 and diethanolamines (RdeaH2) in a 1:2 molar ratio yield monomeric derivatives of the type [BuSn(Rdea)(RdeaH)] (R = H ( 3 ), R = Me ( 4 )). These homometallic complexes on 1:1 reactions with an appropriate metal alkoxide form monomeric heterobimetallic complexes of the type [BuSn (Rdea)2 {M(OR′)n}] (R = H, M = Al, R′ = Pri, n = 2 ( 5 ); R = H, M = Ti, R = Pri, n = 3 ( 6 ); R = H, M = Zr, R′ = Pri, n = 3 ( 7 ); R = Me, M = Al, R′ = Pri, n = 2 ( 8 ); R = Me, M = Ti, R′ = Pri, n = 3 ( 9 ); R = Me, M = Ge, R′ = Et, n = 3 ( 10 )). The driving force behind this work was (i) to explore the utility of homometal complexes ( 1 ) –( 4 ) in assembling a metal alkoxide fragment via a condensation reaction and (ii) to gain insights into the structures of new compounds by NMR spectral data. All of these derivatives have been characterized by elemental analysis, spectroscopic (IR, NMR; 1H, 27Al, and 119Sn) studies, and molecular weight measurements. 119Sn NMR spectral studies indicate that both the homometallic ( 3 ) and ( 4 ) and heterobimetallic ( 5 ) – ( 9 ) complexes exist in a solution in an equilibrium of six- and five-coordinated tin(IV) species. 相似文献
20.
L. Weber C. A. Mast M. H. Scheffer H. Schumann S. Uthmann R. Boese D. Bläser H.-G. Stammler A. Stammler 《无机化学与普通化学杂志》2000,626(2):421-429
Synthesis, Structure, and Reactivity of Functionalized Stibanido Complexes of Iron and Ruthenium [(η5-C5Me5)(CO)2MSbR1R2] (M = Fe, Ru; R1, R2 = SiMe3, C(O) t Bu, C(O)Ph, C(O)-1 Ad) The reaction of equimolar amounts of [(η5-C5Me5)(CO)2RuSb(SiMe3)2] ( 1 b ) and the carboxylic chlorides RC(O)Cl (R = tBu, Ph, 1-adamantyl) afforded the acyl(trimethylsilyl)stibanido complexes [(η5-C5Me5)(CO)2RuSb · {C(O)R}(SiMe3)] 2 b (R = tBu), 4 b (R = Ph), and 6 b (R = 1-Ad). The treatment of 1 b with two molar equivalents of pivaloyl chloride and benzoyl chloride led to the diacylstibanido complexes [(η5-C5Me5)(CO)2RuSb{C(O)R}2] ( 3 b , 5 b ). Analogously, the iron complex [(η5-C5Me5)(CO)2FeSb · (SiMe3)2] ( 1 a ) is converted into the corresponding diacylstibanido complexes 3 a (R = tBu), 5 a (R = Ph) and 7 a (R = 1-Ad) by an excess of acid chloride. The treatment of 1 a with equimolar amounts of RC(O)Cl gave inseparable mixtures of starting material and the monoacyl- and diacyl stibanido complexes. Oxalyl chloride reacted quantitatively with two equivalents of 1 a to give complex [{(η5-C5Me5) · (CO)2FeSb(SiMe3)C(O)}2] ( 8 ). The molecular structures of 1 a , 2 b and 5 b were elucidated by single crystal X-ray analyses. 相似文献