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1.
Hui‐Xian Yeong Dr. Hong‐Wei Xi Dr. Yongxin Li Dr. Sophy Bhasi Kunnappilly Prof. Dr. Bozhen Chen Prof. Dr. Kai‐Chung Lau Prof. Dr. Hajime Hirao Prof. Dr. Kok Hwa Lim Prof. Dr. Cheuk‐Wai So 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14726-14731
The syntheses of a zwitterionic base‐stabilized digermadistannacyclobutadiene and tetragermacyclobutadiene supported by amidinates and low‐valent germanium amidinate substituents are described. The reaction of the amidinate GeI dimer, [LGe:]2 ( 1 , L=PhC(NtBu)2), with two equivalents of the amidinate tin(II) chloride, [LSnCl] ( 2 ), and KC8 in tetrahydrofuran (THF) at room temperature afforded a mixture of the zwitterionic base‐stabilized digermadistannacyclobutadiene, [L2Ge2Sn2L′2] ( 3 ; L′=LGe:), and the bis(amidinate) tin(II) compound, [L2Sn:] ( 4 ). Compound 3 can also be prepared by the reaction of 1 with [LArSnCl] ( 5 , LAr=tBuC(NAr)2, Ar=2,6‐iPr2C6H3) in THF at room temperature. Moreover, the reaction of 1 with the “onio‐substituent transfer” reagent [4‐NMe2‐C5H4NSiMe3]OTf ( 8 ) in THF and 4‐(N,N‐dimethylamino)pyridine (DMAP) at room temperature afforded a mixture of the zwitterionic base‐stabilized tetragermacyclobutadiene, [L4Ge6] ( 9 ), the amidinium triflate, [PhC(NHtBu)2]OTf ( 10 ), and Me3SiSiMe3 ( 11 ). X‐ray structural data and theoretical studies show conclusively that compounds 3 and 9 have a planar and rhombic charge‐separated structure. They are also nonaromatic. 相似文献
2.
Hui‐Xian Yeong Shu‐Hua Zhang Dr. Hong‐Wei Xi Dr. Jing‐Dong Guo Prof. Dr. Kok Hwa Lim Prof. Dr. Shigeru Nagase Prof. Dr. Cheuk‐Wai So 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(9):2685-2691
The synthesis and characterization of new amidinate‐stabilized germatrisilacyclobutadiene ylides [L3Si3GeL′] (L=PhC(NtBu)2; L′=ËL; Ë=Ge ( 3 ), Si ( 7 )) are described. Compound 3 was prepared by the reaction of [LSi? SiL] ( 1 ) with one equivalent of [LGe? GeL] ( 2 ) in THF. Compound 7 was synthesized by the reaction of 2 with excess 1 in THF. The bisamidinate germylene [L2Ge:] ( 4 ) is a by‐product in both reactions. Moreover, compound 7 was prepared by the reaction of 3 with one equivalent of 1 in THF. Compounds 3 and 7 have been characterized by NMR spectroscopy, X‐ray crystallography, and theoretical studies. The results show that compounds 3 and 7 are not antiaromatic. The puckered Si3Ge four‐membered rings in 3 and 7 have a ylide structure, which is stabilized by amidinate ligands and the electron delocalization within the Si3Ge four‐membered ring. 相似文献
3.
Yao S Xiong Y Wang W Driess M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(17):4890-4895
The first isolable pyridine‐stabilized germanone has been prepared and its reactivity toward trimethylaluminum has been investigated. The germanone adduct results from a stepwise conversion that starts from 4‐dimethylaminopyridine (DMAP) and the ylide‐like N‐heterocyclic germylene LGe: (L=CH{(C?CH2)(CMe)[N(aryl)]2}, aryl=2,6‐iPr2C6H3) ( 1 ) at room temperature, and gives the corresponding germylene–pyridine adduct L(DMAP)Ge: ( 2 ) in 91 % yield. The latter reacts with N2O at room temperature to form the desired germanone complex L(DMAP)Ge?O ( 3 ) in 73 % yield. The Ge? O distance of 1.646(2) Å in 3 is the shortest hitherto reported for a Ge?O species. The reaction of 3 with trimethylaluminum leads solely to the addition product LGe(Me)O[Al(DMAP)Me2] ( 4 ). The latter results from insertion of the Ge?O subunit into an Al? Me bond of AlMe3 and concomitant migration of the DMAP ligand from germanium to the aluminum atom. Compounds 2 – 4 have been fully characterized by analytical and spectroscopic methods. Their molecular structures have been established by single‐crystal X‐ray crystallographic analysis. 相似文献
4.
Dr. Shenglai Yao Dr. Yun Xiong Dr. Tibor Szilvási Prof. Dr. Hansjörg Grützmacher Prof. Dr. Matthias Driess 《Angewandte Chemie (International ed. in English)》2016,55(15):4781-4785
The first 4π‐electron resonance‐stabilized 1,3‐digerma‐2,4‐diphosphacyclobutadiene [LH2Ge2P2] 4 (LH=CH[CHNDipp]2 Dipp=2,6‐iPr2C6H3) with four‐coordinate germanium supported by a β‐diketiminate ligand and two‐coordinate phosphorus atoms has been synthesized from the unprecedented phosphaketenyl‐functionalized N‐heterocyclic germylene [LHGe‐P=C=O] 2 a prepared by salt‐metathesis reaction of sodium phosphaethynolate (P≡C?ONa) with the corresponding chlorogermylene [LHGeCl] 1 a . Under UV/Vis light irradiation at ambient temperature, release of CO from the P=C=O group of 2 a leads to the elusive germanium–phosphorus triply bonded species [LHGe≡P] 3 a , which dimerizes spontaneously to yield black crystals of 4 as isolable product in 67 % yield. Notably, release of CO from the bulkier substituted [LtBuGe‐P=C=O] 2 b (LtBu=CH[C(tBu)N‐Dipp]2) furnishes, under concomitant extrusion of the diimine [Dipp‐NC(tBu)]2, the bis‐N,P‐heterocyclic germylene [DippNC(tBu)C(H)PGe]2 5 . 相似文献
5.
Seven square planar bis(o-diiminobenzosemiquinonato)nickel(II) complexes, [Ni(o-C6H4(NH)(NAr))2] (Ar= Mes, 1; p-F-C6H4, 2; p-CI-C6H4, 3), [Ni(o-4,5-F2-C6H2(NH)(NPh))2] (4), and [Ni(o-4,5-CIz-C6H2(NH)(NAr))2] (Ar =Ph, 5; 2,6-F2-C6H3, 6; 2,6-C12-C6H3, 7), have been synthesized and characterized by 1H NMR, 13C NMR, 19F NMR, IR, UV-Vis-NIR, elemental analyses, HRMS, as well as single-crystal X-ray diffraction studies (1 and 7). The cyclic voltammograms of these complexes exhibit two reversible redox processes of [NiLe]0n- and [NIL2]l /2 , and one irreversible process of [NiL2]~n+. Substituent effects on the redox properties of these complexes, in addi- tion with those of the known complexes [Ni(o-C6Ha(NH)(NPh))2] (8) and [Ni(o-3,5-Butz-C6Hz(NH)2)2] (9), are identified by comparing the half-wave potentials of the reduction waves, as 1 ~ 9 〈 8 ~ 2 〈 3 〈 4 〈 5 〈 7 〈 6, reflect- ing the ease of reduction of [NIL2] parallels the electron-donating and -withdrawing ability of the substituent group. Reduction of 1 with one or two equivalents of sodium metal in THF has led to the isolation of [Na(THF)3][I] and [Na(THF)3]2[1]. The structure data of these two complexes revealed by low-temperature X-ray crystallography suggest their corresponding electronic structures of [Nill(lL-1 )(IL2-)]1- and [Ni1](1L2 )212-, which are in line with those of [9]n (n = 1-, 2-) suggested by spectroelectrochemical study. 相似文献
6.
Dr. John A. Kelly Martin Juckel Dr. Terrance J. Hadlington Prof. Dr. Israel Fernández Prof. Dr. Gernot Frenking Prof. Dr. Cameron Jones 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(11):2773-2785
Three amide ligands of varying steric bulk and electronic properties were utilized to prepare a series of amido-germanium(II)/tin(II) halide compounds, (LEX)n, (L= -N{B(DipNCH)2}(SiMe3), TBoL; -N{B(DipNCH)2}(SiPh3), PhBoL; -N(Dip)(tBu), DBuL; Dip=C6H3iPr2-2,6; E=Ge or Sn; X=Cl or Br; n=1 or 2). Reductions of these with a magnesium(I) dimer, {(MesNacnac)Mg}2 (MesNacnac=[(MesNCMe)2CH]−, Mes=mesityl), afforded singly bonded amido-digermynes (TBoLGe−GeTBoL and PhBoLGe−GePhBoL), and an amido-distannyne (PhBoLSn−SnPhBoL), in addition to several low-valent, amido stabilized tetrel–tetrel bonded cluster compounds, (DBuLGe)4, (DBuLSn)6 and Sn5(TBoL)4. The nature of the products resulting from these reactions was largely dependent on the steric bulk of the amide ligand employed. Cluster (DBuLGe)4 possessed an unusual folded butterfly structure, the bonding and electronic of which were examined using DFT calculations. Reactions of the amido-germanium(I) compounds with H2 were explored, and gave rise to the amido-digermene, TBoL(H)Ge=Ge(H)TBoL and the cyclotetragermane, {DBuL(H)Ge}4. Reactions of (DBuLGe)4 with a series of unsaturated small molecule substrates yielded DBuLGeOGeDBuL, DBuLGe(μ-C2H4)2GeDBuL and DBuLGe(μ-1,4-C6H8)(μ-1,2-C6H8)GeDBuL. The latter results imply that (DBuLGe)4 can act as a masked source of the digermyne DBuLGeGeDBuL in these reactions. All further reactivity studies indicated that the germanium(I) compounds exhibit a “transition-metal-like” behavior, which is closely related to that previously described for bulky digermynes and related compounds. 相似文献
7.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(6):769-781
The structural study of Sc complexes containing dianions of anthracene and tetraphenylethylene should shed some light on the nature of rare‐earth metal–carbon bonding. The crystal structures of (18‐crown‐6)bis(tetrahydrofuran‐κO)sodium bis(η6‐1,1,2,2‐tetraphenylethenediyl)scandium(III) tetrahydrofuran disolvate, [Na(C4H8O)2(C12H24O6)][Sc(C26H20)2]·2C4H8O or [Na(18‐crown‐6)(THF)2][Sc(η6‐C2Ph4)2]·2(THF), ( 1b ), (η5‐1,3‐diphenylcyclopentadienyl)(tetrahydrofuran‐κO)(η6‐1,1,2,2‐tetraphenylethenediyl)scandium(III) toluene hemisolvate, [Sc(C17H13)(C26H20)(C4H8O)]·0.5C7H8 or [(η5‐1,3‐Ph2C5H3)Sc(η6‐C2Ph4)(THF)]·0.5(toluene), ( 5b ), poly[[(μ2‐η3:η3‐anthracenediyl)bis(η6‐anthracenediyl)bis(η5‐1,3‐diphenylcyclopentadienyl)tetrakis(tetrahydrofuran)dipotassiumdiscandium(III)] tetrahydrofuran monosolvate], {[K2Sc2(C14H10)3(C17H13)2(C4H8O)4]·C4H8O}n or [K(THF)2]2[(1,3‐Ph2C5H3)2Sc2(C14H10)3]·THF, ( 6 ), and 1,4‐diphenylcyclopenta‐1,3‐diene, C17H14, ( 3a ), have been established. The [Sc(η6‐C2Ph4)2]− complex anion in ( 1b ) contains the tetraphenylethylene dianion in a symmetrical bis‐η3‐allyl coordination mode. The complex homoleptic [Sc(η6‐C2Ph4)2]− anion retains its structure in THF solution, displaying hindered rotation of the coordinated phenyl rings. The 1D 1H and 13C{1H}, and 2D COSY 1H–1H and 13C–1H NMR data are presented for M[Sc(Ph4C2)2]·xTHF [M = Na and x = 4 for ( 1a ); M = K and x = 3.5 for ( 2a )] in THF‐d8 media. Complex ( 5b ) exhibits an unsymmetrical bis‐η3‐allyl coordination mode of the dianion, but this changes to a η4 coordination mode for (1,3‐Ph2C5H3)Sc(Ph4C2)(THF)2, ( 5a ), in THF‐d8 solution. A 45Sc NMR study of ( 2a ) and UV–Vis studies of ( 1a ), ( 2a ) and ( 5a ) indicate a significant covalent contribution to the Sc—Ph4C2 bond character. The unique Sc ate complex, ( 6 ), contains three anthracenide dianions demonstrating both a η6‐coordination mode for two bent ligands and a μ2‐η3:η3‐bridging mode of a flat ligand. Each [(1,3‐Ph2C5H3)2Sc2(C14H10)3]2− dianionic unit is connected to four neighbouring units via short contacts with [K(THF)2]+ cations, forming a two‐dimensional coordination polymer framework parallel to (001). 相似文献
8.
Reaction of potassium salt of N‐aryliminopyrrole ligand [2‐(2, 6‐iPr2C6H3N=CH)–C4H3NK] ( 1 ) with samarium tris‐boro‐hydride [Sm(BH4)3(THF)3] gave a samarium ate complex [η2‐{2‐(2, 6‐iPr2C6H3N=CH)–C4H3N}3Sm(η1‐BH4){K(THF)6] ( 2 ); whereas similar treatment with erbium borohydride [Er(BH4)3(THF)3] afforded the mono(iminopyrrolyl) complex [η2‐{2‐(2, 6‐iPr2C6H3N=CH)–C4H3N}Er(η3‐BH4)2(THF)2] ( 3 ). In the solid‐state structures, the samarium complex 2 shows a rarely observed η1 and the erbium complex 3 shows a usual η3 coordination mode of the borohydrido ligand. 相似文献
9.
The synthesis, characterization and methyl methacrylate polymerization behaviors of 2‐(N‐arylimino)pyrrolide nickel complexes are described. The nickel complex [NN]2Ni ( 1 , [NN] = [2‐C(H)NAr‐5‐tBu‐C4H2N]?, Ar = 2,6‐iPr2C6H3) was prepared in good yield by the reaction of [NN]Li with trans‐[Ni(Cl)(Ph)(PPh3)2] in THF. Reaction of [NN]Li with NiBr2(DME) yielded the nickel bromide [NN]Ni(Br)[NNH] ( 2 ). Complexes 1 and 2 were characterized by 1H NMR and IR spectroscopy and elemental analysis, and by X‐ray single crystal analysis. Both complexes, upon activation with methylaluminoxane, are highly active for the polymerization of methyl methacrylate to give high molecular weight polymethylmethacrylate with narrow molecular distributions. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
10.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(26):7573-7577
A facile, one‐pot synthesis of [Na(OC≡As)(dioxane)x ] (x =2.3–3.3) in 78 % yield is reported through the reaction of arsine gas with dimethylcarbonate in the presence of NaOt Bu and 1,4‐dioxane. It has been employed for the synthesis of the first arsaketenyl‐functionalized germylene [LGeAsCO] ( 2 , L=CH[CMeN(Dipp)]2; Dipp=2,6‐i Pr2C6H3) from the reaction with LGeCl ( 1 ). Upon exposure to ambient light, 2 undergoes CO elimination to form the 1,3‐digerma‐2,4‐diarsacyclobutadiene [L2Ge2As2] ( 3 ), which contains a symmetric Ge2As2 ring with ylide‐like Ge=As bonds. Remarkably, the CO ligand located at the arsenic center of 2 can be exchanged with PPh3 or an N‐heterocyclic carbene i PrNHC donor (i PrNHC=1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) to afford the novel germylidenylarsinidene complexes [LGe‐AsPPh3] ( 4 ) and [LGe‐As(i PrNHC)] ( 5 ), respectively, demonstrating transition‐metal‐like ligand substitution at the arsinidene‐like As atom. The formation of 2 – 5 and their electronic structures have been studied by DFT calculations. 相似文献
11.
Dominik Vítek Prof. Aleš Růžička Lise Vermeersch Dr. Libor Dostál Dr. Jan Turek Prof. Roman Jambor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202202639
Reactivity studies of the GeII→B complex L(Cl)Ge⋅BH3 ( 1 ; L=2-Et2NCH2-4,6-tBu2-C6H2) were performed to determine the effect on the GeII→B donation. N-coordinated compounds L(OtBu)Ge⋅BH3 ( 2 ) and [LGe⋅BH3]2 ( 3 ) were prepared. The possible tuning of the GeII→B interaction was proved experimentally, yielding compounds 1-PPh2-8-(LGe)-C10H6 ( 4 ) and L(Cl)Ge⋅GaCl3 ( 5 ) without a GeII→B interaction. In 5 , an unprecedented GeII→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1 − 5 . The different strength of the GeII→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed. 相似文献
12.
Michael A. Shestopalov Olga A. Efremova Anton I. Smolentsev Yuri V. Mironov Vladimir E. Fedorov Yong‐Won Song 《Helvetica chimica acta》2011,94(10):1786-1791
A new germanium complex, cis‐[Ge(pyca)2(OH)2]?2 H2O ( 1 ; pyca=pyridine‐2‐carboxylato), was synthesized by the reaction of [Ge(acac)2Cl2] (acac=acetylacetonato=pentane‐2,4‐dionato) with potassium pyridine‐2‐carboxylate (Kpyca) in H2O/THF. According to the single‐crystal X‐ray diffraction analysis, each Ge‐atom of 1 is coordinated by two pyca ligands and two OH? groups (Fig. 1). These molecules are bonded to each other via a system of H‐bonds resulting in a sheet‐like structure (Fig. 2). The complex is decomposed during heating with stepwise mass loss and formation of GeO2 as final product (Fig. 3). 相似文献
13.
The steric effect of an aryloxido group on the synthesis and molecular structures of ytterbium aryloxides supported by β‐diketiminato ligand L (L = [N(2,6‐Me2C6H3)C(Me)]2CH?) is reported. Reactions of β‐diketiminatoytterbium dichloride, LYbCl2(THF)2, with NaOAr1 in THF (Ar1 = [2,6‐tBu2‐4‐MeC6H2], THF = tetrahydrofuran) at 60°C gave the corresponding ytterbium complexes LYb(OAr1)Cl(THF) ( 1 ) and LYb(OAr1)2 (1), depending on the molar ratio of dichloride to sodium aryloxide, respectively, while the same reactions with NaOAr2 and NaOAr3 (Ar2 = [2,6‐iPr2C6H3], Ar3 = [2,6‐Me2C6H3]) in 1:1 or 1:2 molar ratio in THF afforded only bisaryloxide complexes LYb(OAr2)2(THF) (1) and LYb(OAr3)2(THF) ( 4 ) in good yields, respectively. Complexes 1 , 2 , 3 , 4 were fully characterized, including X‐ray crystal structure analyses. All the complexes are efficient pre‐catalysts for the catalytic addition of amines to carbodiimides giving guanidines. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
14.
B. Rke F. Zülch Y. Ding J. Prust H. W. Roesky M. Noltemeyer H.‐G. Schmidt 《无机化学与普通化学杂志》2001,627(5):836-840
Synthesis, Structure, and Properties of [nacnac]MX3 Compounds (M = Ge, Sn; X = Cl, Br, I) Reactions of [nacnac]Li [(2,6‐iPr2C6H3)NC(Me)C(H)C(Me)N(2,6‐iPr2C6H3)]Li ( 1 ) with SnX4 (X = Cl, Br, I) and GeCl4 in Et2O resulted in metallacyclic compounds with different structural moieties. In the [nacnac]SnX3 compounds (X = Cl 2 , Br 3 , I 4 ) the tin atom is five coordinated and part of a six‐membered ring. The Sn–N‐bond length of 3 is 2.163(4) Å and 2.176(5) Å of 4 . The five coordinated germanium of the [nacnac]GeCl3 compound 5 shows in addition to the three chlorine atoms further bonds to a carbon and to a nitrogen atom. In contrast to the known compounds with the [nacnac] ligand the afore mentioned reaction creates a carbon–metal‐bond (1.971(3) Å) forming a four‐membered ring. The Ge–N bond length (2.419(2) Å) indicates the formation of a weakly coordinating bond. 相似文献
15.
1,1‐Diethyl‐1‐germa‐2,3,4,5‐tetra‐ tert ‐butyl‐2,3,4,5‐tetraphospholane (C2H5)2Ge( t BuP)4, Molecular and Crystal Structure The reaction of the diphosphide K2[(tBuP)4] · THF ( 1 ) with the germanium(IV) compound (C2H5)2GeCl2 leads via a [4 + 1]‐cyclo‐condensation reaction to 1,1‐diethyl‐1‐germa‐2,3,4,5‐tetra‐tert‐butyl‐2,3,4,5‐tetraphospholane (C2H5)2Ge(tBuP)4 ( 2 ) with the 5‐membered GeP4 ring system. 2 could be characterized 31P NMR spectroscopically, mass spectrometrically and by a single crystal structure analysis. 相似文献
16.
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
17.
Simplicio Gonzlez‐Montiel Raymundo Cea‐Olivares Vojtech Jancik Leslie W. Pineda Rubn A. Toscano 《Heteroatom Chemistry》2009,20(1):45-49
The spiro‐dibenzogermocine [O(o‐C6H4S)2]2Ge ( 1 ) was prepared in a reaction between O(o‐C6H4SH)2 and Ge(OiPr)4, and its molecular structure was determined by X‐ray diffraction studies. In the solid state, 1 shows the existence of two weak O → Ge transannular interactions, resulting in a hexacoordinated germanium atom that displays the geometry of a distorted bicapped tetrahedron. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:45–49, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20510 相似文献
18.
M. T. Duarte V. Gama S. Rabaa I. C. Santos 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(7):m278-m280
The title compound, [Fe(C10H15)2][Ni(C3OS4)2]·C4H8O or [Fe(Cp*)2][Ni(dmio)2]·THF, where [Fe(Cp*)2]+ is the decamethylferrocenium cation, dmio is the 2‐oxo‐1,3‐dithiole‐4,5‐dithiolate dianion and THF is tetrahydrofuran, crystallizes with two independent half‐anion units [one Ni atom is at the centre of symmetry (, , 0) and the other is at the centre of symmetry (, 0, )], one cation unit (located in a general position) and one THF solvent molecule in the asymmetric unit. The crystal structure consists of two‐dimensional layers composed of parallel mixed chains, where pairs of cations alternate with single anions. These layers are separated by sheets of anions and THF molecules. 相似文献
19.
Karm Hans Masood Parvez Sumera Mahboob Imtiaz‐ud‐Din Muhammad Mazhar Saqib Ali 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(11):m559-m562
The central Ge atoms in the structures of 3‐(2‐fluorophenyl)‐3‐(triphenylgermyl)propionic acid, [Ge(C6H5)3(C9H8FO2)], 3‐(2‐tolyl)‐3‐(tri‐4‐tolylgermyl)propionic acid, [Ge(C7H7)3(C10H11O2)], and 3‐(4‐tolyl)‐3‐(tribenzylgermyl)propionic acid, [Ge(C7H7)3(C10H11O2)], are four‐coordinate with slightly distorted tetrahedral geometry. The Ge—Csp3 distances [1.970 (3)–1.997 (3) Å] are significantly longer than the Ge—Caromatic distances [1.940 (3)–1.959 (2) Å]. In all three structures, the molecules form dimeric pairs about inversion centres through strong hydrogen‐bonding interactions between carboxylic acid groups. 相似文献
20.
Miroslav Novák Marek Bouška Dr. Libor Dostál Dr. Aleš Růžička Dr. Alexander Hoffmann Prof. Dr. Sonja Herres‐Pawlis Dr. Roman Jambor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(21):7820-7829
We report here the synthesis of new C,N‐chelated chlorostannylenes and germylenes L3MCl (M=Sn( 1 ), Ge ( 2 )) and L4MCl (M=Sn( 3 ), Ge ( 4 )) containing sterically demanding C,N‐chelating ligands L3, 4 (L3=[2,4‐di‐tBu‐6‐(Et2NCH2)C6H2]?; L4=[2,4‐di‐tBu‐6‐{(C6H3‐2′,6′‐iPr2)N=CH}C6H2]?). Reductions of 1 – 4 yielded three‐coordinate C,N‐chelated distannynes and digermynes [L3, 4M ]2 for the first time ( 5 : L3, M=Sn, 6 : L3, M=Ge, 7 : L4, M=Sn, 8 : L4, M=Ge). For comparison, the four‐coordinate distannyne [L5Sn]2 ( 10 ) stabilized by N,C,N‐chelate L5 (L5=[2,6‐{(C6H3‐2′,6′‐Me2)N?CH}2C6H3]?) was prepared by the reduction of chlorostannylene L5SnCl ( 9 ). Hence, we highlight the role of donor‐driven stabilization of tetrynes. Compounds 1 – 10 were characterized by means of elemental analysis, NMR spectroscopy, and in the case of 1 , 2 , 5 – 7 , and 10 , also by single‐crystal X‐ray diffraction analysis. The bonding situation in either three‐ or four‐coordinate distannynes 5 , 7 , and 10 was evaluated by DFT calculations. DFT calculations were also used to compare the nature of the metal–metal bond in three‐coordinate C,N‐chelating distannyne [L3Sn]2 ( 5 ) and related digermyme [L3Ge]2 ( 6 ). 相似文献