Divalent germanium compound with a radical-anionic ligand: molecular structures of (dpp-BIAN)*- GeCl and its hydrochloration products [(dpp-BIAN)(H)2]*+ [GeCl3]- and [[(dpp-BIAN)(H)2*+]2(Cl-)]+ [GeCl3]- (dpp-BIAN=1,2-Bis[(2,6-diisopropylphenyl)imino]acenaphthene)

The germanium(II) compound (dpp-BIAN)GeCl (1), which contains the radical anion of dpp-BIAN can be prepared either by reacting free dpp-BIAN ligand with 2 equiv of GeCl2(1,4-dioxane) in Et2O or by metathetical reaction of the sodium salt of dpp-BIAN with germanium dichloride in Et2O or benzene. The reaction of benzene solutions of 1 with 2 or 3 equiv of HCl led to protonation of the dpp-BIAN ligand affording [(dpp-BIAN)(H)2]*+[GeCl3]- (2) and [[(dpp-BIAN)(H)2*+]2(Cl-)]+ [GeCl3]- (3), which incorporate the radical cation of the protonated ligand. Compounds 1-3 have been characterized by elemental analysis, IR, UV-vis, and electron spin resonance (ESR) spectroscopy. Molecular structures of 1-3 were determined by single-crystal X-ray diffraction. In molecule 1, the Ge atom is positioned at the apex of the slightly distorted trigonal pyramid. The Ge-N bond lengths in 1 are 2.0058(19) and 2.004(2) A. The molecular structure of 2 consists of contact ions [(dpp-BIAN)(H)2]+ and [GeCl3]-. In the molecular structure of 3, two radical cations of [(dpp-BIAN)(H)2]+ are "coordinated" by the chlorine anion. The ESR signal of 1 indicates the presence of a dpp-BIAN radical anion and shows a hyperfine structure due to the coupling of an unpaired electron to 14N, 73Ge, 35Cl, 37Cl, and 1H nuclei (AN=0.48 (2 N), AGe=0.96, ACl=0.78 (35Cl), ACl=0.65 (37Cl), AH=0.11 (4 H) mT, g=2.0014). Both 2 and 3 reveal ESR signals of radical cation [(dpp-BIAN)(H)2]*+ (septet, AN=0.53, AH=0.48 mT, g=2.0031).     

Electrodeposition of Ge, Si and Si x Ge 1-x from an air- and water-stable ionic liquid

The electrodeposition of Ge, Si and, for the first time, of Si(x)Ge(1-x) from the air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py(1,4)]Tf(2)N) containing GeCl(4) and/or SiCl(4) as precursors is investigated by cyclic voltammetry and high-resolution scanning electron microscopy. GeCl(2) in [Py(1,4)]Tf(2)N is electrochemically prepared in a two-compartment cell to be used as Ge precursor instead of GeCl(4) in order to avoid the chemical attack of Ge(iv) on deposited Ge. Silicon, germanium and Si(x)Ge(1-x) can be deposited reproducibly and easily in this ionic liquid. Interestingly, the Si(x)Ge(1-x) deposit showed a strong colour change (from red to blue) at room temperature during electrodeposition, which is likely to be due to a quantum size effect. The observed colours are indicative of band gaps between at least 1.5 and 3.2 eV. The potential of ionic liquids in Si(x)Ge(1-x) electrodeposition is demonstrated.     

Synthesis, characterisation and reactivity of germanium(II) amidinate and guanidinate complexes

Reactions of lithium salts of the bulky guanidinate ligands, [ArNC(NR2)NAr](-) (NR2 = N(C6H11)2 (Giso-) and cis-NC5H8Me2-2,6 (Pipiso-); Ar = C6H3Pri2-2,6), with GeCl2.dioxane afforded the heteroleptic germylenes, [(Giso)GeCl] and [(Pipiso)GeCl], the former of which was structurally characterised. The further reactivity of these and the related complexes, [(Piso)GeCl] and [(Priso)GeCl] (Piso- = [ArNC(Bu(t))NAr]-, Priso- = [ArNC(NPri2)NAr]-) has been investigated. Salt elimination reactions have yielded the new monomeric complexes, [(Piso)Ge(NPri2)] and [(Piso)GeFeCp(CO)2], whilst a ligand displacement reaction afforded the heterometallic species, [(Piso)Ge(Cl)(W(CO)5)]. Chloride abstraction from [(Priso)GeCl] with GaCl3 has given the structurally characterised contact ion pair, [(Priso)Ge][GaCl4]. In addition, the inconclusive outcome of a number of attempts to reduce the germanium halide complexes are discussed.     

Novel hypervalent complexes of main-group metals by intramolecular ligand-->metal electron transfer

New fascinating electronic features of the simple diketoamine chelate ligand HN[CH2C(tBu)=O]2 (1) are described. Unexpectedly, the corresponding trianionic amido-dienolate form of 1 is capable of reducing main-group metal atoms M after initial coordination and intramolecular L-->M two-electron transfer and of stabilizing main-group elements in unusual low oxidation states. This is impressively shown by the synthesis and structural characterization of the novel Ge and Sn complexes 4-6 by redox reactions of lithiated 1 with the corresponding metal halides GeCl4 and MCl2 (M=Ge, Sn). Surprisingly, conversion of tris-lithiated 1 with GeCl4 readily consumes two molar equivalents of GeCl4 and results in the formation of the neutral GeCl3 complex 4 and GeCl2. The former represents the second example of a structurally characterized neutral octahedrally coordinated germanium compound. Reaction of dilithiated 1 with GeCl2 does not lead to the expected ClGe(+2) complex but affords the novel dimeric germylene 5, whereas similar reaction using SnCl2 furnishes the monomeric stannylene (ClSn(+2) complex) 2 and elemental tin due to the higher oxidation potential of Sn(+2). Unexpectedly, a similar redox reaction of dilithiated 1 with PbCl2 furnishes the first air- and water-stable lithium 1,2-diketoimine-enolate 7 and elemental lead. Compound 7 is tetrameric in the solid state and consists of a strongly distorted Li4O4 cubic core with trigonal-bipyramidal coordinated Li+ ions.     

In situ Ge-Ge bond formation under ambient conditions: synthesis, characterization and reactivity of organo-functionalized telluridogermanate complexes

Unprecedented noradamantane-type compounds [(R(2,3)Ge)(4)Te(5)] (R(2) = CH(2)CH(2)COOH, R(3) = CH(CH(2)COOH)(2)), containing a Ge-Ge bond, yield from reactions of R(2,3)GeCl(3) with Na(2)Te or Li(2)Te in THF, while reactions with R(1)GeCl(3) (R(1) = CMe(2)CH(2)COMe) afford a double-decker-type cage [(R(3)Ge)(4)Te(6)]; by reaction with hydrazine, the latter reacts to the hydrazone functionalized, monomeric anion [(R(4)Ge)Te(2)](-) (R(4) = CMe(2)CH(2)CNNH(2)Me).     

Aminotroponiminatogermaacid halides with a ge(e)x moiety (e = s, se; x = f, cl)

Fluorination of aminotroponiminate (ATI) ligand-stabilized germylene monochloride [(t-Bu)(2)ATI]GeCl (1) with CsF gave the aminotroponiminatogermylene monofluoride [(t-Bu)(2)ATI]GeF (2). Oxidative addition reaction of compound 2 with elemental sulfur and selenium led to isolation of the corresponding germathioacid fluoride [(t-Bu)(2)ATI]Ge(S)F (3) and germaselenoacid fluoride [(t-Bu)(2)ATI]Ge(Se)F (4), respectively. Similarly, reaction of aminotroponiminatogermylene monochloride [(i-Bu)(2)ATI]GeCl (9) with elemental sulfur and selenium gave the aminotroponiminatogermathioacid chloride [(i-Bu)(2)ATI]Ge(S)Cl (11) and aminotroponiminatogermaselenoacid chloride [(i-Bu)(2)ATI]Ge(Se)Cl (12), respectively. Compound 9 has been prepared through a multistep synthetic route starting from 2-(tosyloxy)tropone 5. All compounds (2-4 and 6-12) were characterized through the multinuclear NMR spectroscopy, and single-crystal X-ray diffraction studies were performed on compounds 2, 4, and 8-12. The germaselenoacid halide complexes 4 and 12 showed doublet (-142.37 ppm) and singlet (-213.13 ppm) resonances in their (77)Se NMR spectra, respectively. Germylene monohalide complexes 2 and 9 have a germanium center in distorted trigonal pyramidal geometry, whereas a distorted tetrahedral geometry is seen around the germanium center in germaacid halide complexes 4, 11, and 12. The length of the Ge═E bond in germathioacid chloride (11) and germaselenoacid halide (4 and 12) complexes is 2.065(1) and 2.194(av) ?, respectively. Theoretical studies (based on the DFT methods) on complexes 4, 11, and 12 reveal the nature of the Ge═E multiple bond in these germaacid halide complexes with computed Wiberg bond indices (WBI) being 1.480, 1.508, and 1.541, respectively.     

Theoretical designs for germaacetylene (RC≡GeR'): a new target for synthesis

The effect of substitution on the potential energy surfaces of RC≡GeR (R = F, H, OH, CH(3), SiH(3), Tbt, Ar*, SiMe(SitBu(3))(2) and SiiPrDis(2)) was explored using density functional theories (B3LYP/LANL2DZdp and B3PW91/6-31G(d)). Our theoretical studies indicate that all the triply bonded RC≡GeR species prefer to adopt trans-bent geometry, which is in agreement with the theoretical model (mode (B)). Additionally, we show that the stabilities of the RC≡GeR species bearing smaller substituents (R = F, H, OH, CH(3) and SiH(3)) decrease in the order R(2)C=Ge: > RC≡GeR > :C=GeR(2). On the other hand, the triply bonded RC≡GeR molecules with bulkier substituents (R = Tbt, Ar*, SiMe(SitBu(3))(2), SiiPrDis(2)) were found to possess the global minimum on the singlet potential energy surface and are both kinetically and thermodynamically stable. That is to say, both electronic and steric effects of bulky substituents play a crucial role in making triply bonded germaacetylenes (RC≡GeR) an interesting synthetic target.     

Complexes of germanium(IV) fluoride with phosphane ligands: structural and spectroscopic authentication of germanium(IV) phosphane complexes

The first phosphane complexes of germanium(iv) fluoride, trans-[GeF(4)(PR(3))(2)] (R = Me or Ph) and cis-[GeF(4)(diphosphane)] (diphosphane = R(2)P(CH(2))(2)PR(2), R = Me, Et, Ph or Cy; o-C(6)H(4)(PR(2))(2), R = Me or Ph) have been prepared from [GeF(4)(MeCN)(2)] and the ligands in dry CH(2)Cl(2) and characterised by microanalysis, IR, Raman, (1)H, (19)F{(1)H} and (31)P{(1)H} NMR spectroscopy. The crystal structures of [GeF(4)(diphosphane)] (diphosphane = Ph(2)P(CH(2))(2)PPh(2) and o-C(6)H(4)(PMe(2))(2)) have been determined and show the expected cis octahedral geometries. In anhydrous CH(2)Cl(2) solution the complexes are slowly converted into the corresponding phosphane oxide adducts by dry O(2). The apparently contradictory literature on the reaction of GeCl(4) with phosphanes is clarified. The complexes trans-[GeCl(4)(AsR(3))(2)] (R = Me or Et) are obtained from GeCl(4) and AsR(3) either without solvent or in CH(2)Cl(2), and the structures of trans-[GeCl(4)(AsEt(3))(2)] and Et(3)AsCl(2) determined. Unexpectedly, the complexes of GeF(4) with arsane ligands are very unstable and have not been isolated in a pure state. The behaviour of the germanium(iv) halides towards phosphane and arsane ligands are compared with the corresponding silicon(iv) and tin(iv) systems.     

Electrodeposition of germanium from supercritical fluids

Several Ge(II) and Ge(IV) compounds were investigated as possible reagents for the electrodeposition of Ge from liquid CH(3)CN and CH(2)F(2) and supercritical CO(2) containing as a co-solvent CH(3)CN (scCO(2)) and supercritical CH(2)F(2) (scCH(2)F(2)). For Ge(II) reagents the most promising results were obtained using [NBu(n)(4)][GeCl(3)]. However the reproducibility was poor and the reduction currents were significantly less than the estimated mass transport limited values. Deposition of Ge containing films was possible at high cathodic potential from [NBu(n)(4)][GeCl(3)] in liquid CH(3)CN and supercritical CO(2) containing CH(3)CN but in all cases they were heavily contaminated by C, O, F and Cl. Much more promising results were obtained using GeCl(4) in liquid CH(2)F(2) and supercritical CH(2)F(2). In this case the reduction currents were consistent with mass transport limited reduction and bulk electrodeposition produced amorphous films of Ge. Characterisation by XPS showed the presence of low levels of O, F and C, XPS confirmed the presence of Ge together with germanium oxides, and Raman spectroscopy showed that the as deposited amorphous Ge could be crystallised by the laser used in obtaining the Raman measurements.     

{Ge10Si[Si(SiMe3)3]4(SiMe32)Me}-: a Ge10Si framework reveals a structural transition onto elemental germanium

The reaction of the metastable high temperature molecule GeCl synthesized via a co-condensation technique with LiSi(SiMe(3))3 leads to a metalloid Ge(10)Si cluster compound, in which the arrangement of the germanium atoms can be seen as a cutout from the structure of elemental germanium.     

关于合成Ge—132所用Ge原料其残留无机锗的问题

Ｇｅ－１３２中的无机锗含量是一个重要的质量指标。它主要来自ＧｅＨＣｌ３中的ＧｅＣｌ４,而无论哪种锗原料合成Ｇｅ－１３２,ＧｅＨＣｌ３都是中间产物。与用金属Ｇｅ和ＧｅＯ２制备Ｇｅ－１３２的工艺比较,用ＧｅＯ２的盐酸溶液比用金属Ｇｅ在高温下与ＨＣｌ气反应制备ＧｅＨＣｌ３更利于降低Ｇｅ－１３２中残留的无机锗含量。     

Germanium(II)-mediated reductive cross-aldol reaction of bromoaldehydes with aldehydes: NMR studies and ab initio calculations

A highly practical reductive cross-aldol reaction of alpha-bromoaldehydes with various aldehydes has been developed using Ge(II)Cl 2 to produce aldehyde germanium(IV) aldolates, which were directly transformed to various multifunctionalized compounds. A remarkable change in stereoselectivity depended on the alpha-bromoaldehydes employed; secondary alpha-bromoaldehydes gave syn selectivities, while tertiary alpha-bromoaldehydes accomplished the synthesis of anti-selective aldol products with a quaternary carbon center. NMR studies and X-ray analysis strongly suggested the formation of germanium enolate in the reaction of alpha-bromoaldehyde 2h with GeCl 2-dioxane. Detailed mechanistic studies, including NMR analysis and ab initio calculations, revealed the generation of stable germanium aldolates, which was due to the remarkably low Lewis acidity of the germanium(IV).     

Supramolecular assemblies of germanium(II) halides with O-, S- and Se-donor macrocycles - the effects of donor atom type upon structure

Reaction of [GeCl(2)(dioxane)] with [18]aneS(6) (1,4,7,10,13,16-hexathiacyclooctadecane) gives the neutral [GeCl(2)([18]aneS(6))] which forms a supramolecular sheet network involving exocyclic coordination, with the macrocycles bridging Ge atoms which are in a pseudo-trigonal bipyramidal environment from two Cl and two S atoms (saw-horse), with one lone pair assumed to occupy the remaining equatorial void. Conversely, using the mixed S/O macrocycles [18]aneS(3)O(3) (1,4,7-trithia-10,13,16-trioxacyclooctadecane) and [15]aneS(2)O(3) (1,4-dithia-7,10,13-trioxacyclopentadecane) (L) leads to the monocationic pentagonal pyramidal [GeCl(L)](+) whose structures show endocyclic Ge coordination, and displacement of one Cl. The Ge-S and Ge-O bond lengths are surprisingly disparate in these two complexes, and in the former the coordinated Cl is axial, while in the latter it occupies the pentagonal plane (with an S atom axial). Cyclic selenoethers form one-dimensional or two-dimensional supramolecular assemblies with Ge(ii) halides, including [GeCl(2)([8]aneSe(2))] ([8]aneSe(2) = 1,5-diselenacyclooctane), [(GeCl(2))(2)([16]aneSe(4))] ([16]aneSe(4) = 1,5,9,13-tetraselenacyclohexadecane), [GeBr(2)([16]aneSe(4))] and [(GeI(2))(2)([16]aneSe(4))]·GeI(4)- these represent the first germanium species with selenoether ligation. Structural studies on each of these show exocyclic GeX(2) coordination, giving networks based upon Se(2)X(2) coordination at Ge(ii) with a distorted pseudo-trigonal bipyramidal environment in which the Ge-based lone pair is assumed to occupy the vacant equatorial vertex. Further weak GeX contacts are also evident in some cases. The weak, secondary GeS/Se and GeX interactions that pervade these systems may be regarded as a further type of supramolecular interaction allowing assembly of new network structures, and the long II contacts evident between the GeI(2) and GeI(4) units in [(GeI(2))(2)([16]aneSe(4))]·GeI(4) probably provide a small thermodynamic contribution leading to co-crystallisation of ordered GeI(4) molecules within the network.     

Formation of [Ar*Ge(CH2C(Me)C(Me)CH2)CH2C(Me)=]2 (Ar* = C6H3-2,6-Trip2; Trip = C6H2-2,4,6-i-Pr3) via reaction of Ar*GeGeAr* with 2,3-dimethyl-1,3-butadiene: evidence for the existence of a germanium analogue of an alkyne

The reduction of Ar*GeCl (Ar* = C6H3-2,6-Trip2; Trip = C6H2-2,4,6-i-Pr3) with one equivalent of potassium leads to the formation of a germanium analogue of an alkyne Ar*GeGeAr* 1; reaction of 1 with 2,3-dimethyl-1,3-butadiene yields [Ar*Ge(CH2C(Me)C(Me)CH2)CH2C(Me)=]2 2, which was structurally characterized.     

1H, 13C, and 73Ge NMR spectral analysis of substituted aryltrimethylgermanes

NMR chemical shifts of 1H, 13C, and 73Ge are reported for a series of monosubstituted aromatic trimethylgermanes of the type XC6H4Ge(CH3)3; X = p-N(CH3)2, p-OCH3, p-OC2H5, p-C(CH3)3, p-Si(CH3)3, p-Ge(CH3)3, p-Sn(CH3)3, p-CH3, m-CH3, -H, m-OCH3, p-Cl, p-Br, m-F, m-CF3, p-CF3, o-OCH3, and o-CH3. The relatively narrow 73Ge resonances show a strong correlation with Hammett sigma constants, with a correlation coefficient of 0.976 and 0.876 for 73Ge chemical shifts in meta- and para-substituted derivatives, respectively. The 13C chemical shifts of the methyl carbons bonded to germanium also display a relationship, with correlation coefficients of 0.904, 0.993, and 0.911 for para-, meta- and all derivatives, respectively. Comparisons of the Hammett plots for the homologous series XC6H4M(CH3)3; M = C, Si, Ge, Sn, show that, in general, correlation coefficients decrease while slopes increase significantly down the group, presumably reflecting the corresponding increase in chemical shift range of the group 14 atom. The Hammett constant derived for the p-Ge(CH3)3 group of +0.13 compares with the NMR-derived constants of -0.12 for p-C(CH3)3, +0.14 for p-Si(CH3)3, and -0.14 for p-Sn(CH3)3. The indication of electron release by carbon and tin can be rationalized through traditional hyperconjugative arguments for carbon and by the low electronegativity and consequent inductive effect of tin. The small electron attraction suggested by the positive constants for silicon and germanium can be simply, and perhaps naively, attributed to pi-acceptor interactions with the benzene ring.     

A neutral, monomeric germanium(I) radical

Stoichiometric reduction of the bulky β-diketiminato germanium(II) chloride complex [((But)Nacnac)GeCl] ((But)Nacnac = [{N(Dip)C(Bu(t))}(2)CH](-), Dip = C(6)H(3)Pr(i)(2)-2,6) with either sodium naphthalenide or the magnesium(I) dimer [{((Mes)Nacnac)Mg}(2)] ((Mes)Nacnac = [(MesNCMe)(2)CH](-), Mes = mesityl) afforded the radical complex [((But)Nacnac)Ge:](?) in moderate yields. X-ray crystallographic, EPR/ENDOR spectroscopic, computational, and reactivity studies revealed this to be the first authenticated monomeric, neutral germanium(I) radical.     

Extremely bulky amido-group 14 element chloride complexes: potential synthons for low oxidation state main group chemistry

The preparation of a series of extremely bulky secondary amines, Ar*N(H)SiR(3) (Ar* = C(6)H(2){C(H)Ph(2)}(2)Me-2,6,4; R(3) = Me(3), MePh(2) or Ph(3)) is described. Their deprotonation with either LiBu(n), NaH or KH yields alkali metal amide complexes, several monomeric examples of which, [Li(L){N(SiMe(3))(Ar*)}] (L = OEt(2) or THF), [Na(THF)(3){N(SiMe(3))(Ar*)}] and [K(OEt(2)){N(SiPh(3))(Ar*)], have been crystallographically characterised. Reactions of the lithium amides with germanium, tin or lead dichloride have yielded the first structurally characterised two-coordinate, monomeric amido germanium(II) and tin(II) chloride complexes, [{(SiR(3))(Ar*)N}ECl] (E = Ge or Sn; R = Me or Ph), and a chloride bridged amido-lead(II) dimer, [{[(SiMe(3))(Ar*)N]Pb(μ-Cl)}(2)]. DFT calculations on [{(SiMe(3))(Ar*)N}GeCl] show its HOMO to exhibit Ge lone pair character and its LUMO to encompass its Ge based p-orbital. A series of bulky amido silicon(IV) chloride complexes have also been prepared and several examples, [{(SiR(3))(Ar*)N}SiCl(3)] (R(3) = Me(3), MePh(2)) and [{(SiMe(3))(Ar*)N}SiHCl(2)], were crystallographically characterised. The sterically hindered group 14 complexes reported in this study hold significant potential as precursors for kinetically stabilised low oxidation state and/or low coordination number group 14 complexes.     

Alkylation of Deltahedral Zintl clusters: synthesis of [R-Ge9-Ge9-R]4- (R = tBu, sBu, nBu, tAm and structure of [tBu-Ge9-Ge9-tBu]4-

Reactions of nine-atom deltahedral clusters (Zintl ions) of germanium, Ge9n- (n = 2, 3, 4), with alkyl chlorides, RCl (R = tBu, nBu, sBu, tAm), yielded the corresponding dialkylated dimers of Ge9 clusters [R-Ge9-Ge9-R]4-. The tBu derivative with [K(2,2,2-crypt)]+ countercations was characterized in the solid state by single-crystal X-ray diffraction as [K(2,2,2-crypt)]4[tBu-Ge9-Ge9-tBu].7en (monoclinic, C2/c, a = 35.0914(10) A, b = 24.8161(6) A, and c = 16.8782(5) A, beta = 94.0136(17) degrees , V = 14662.0(7) A3, and Z = 4) and in solution by 1H and 13C NMR. All species were also characterized in solution by electrospray mass spectrometry in the negative-ion mode. These are the first main group deltahedral clusters functionalized with purely organic substituents.     

Reactions of LiE(SiMe(3))(3), E = Si, Ge: X-ray Crystal Structure of the Cyclotetrastannane [ClSnSi(SiMe(3))(3)](4)

Reaction of SnCl(2).dioxane with 2 equiv of Li(THF)(3)Si(SiMe(3))(3) in hexane afforded the cyclotetrastannane [(Me(3)Si)(3)SiSnCl](4) in reasonable yield. From pentane, the product crystallized as a red-orange disolvate in the P&onemacr; space group (triclinic) with a = 14.735(2) ?, b = 14.976(2) ?, c = 24.066(3) ?, alpha = 76.94 degrees, beta = 76.19 degrees, gamma = 62.11 degrees, V = 4517.5 ?(3), and Z = 2. The Sn(4) ring consisted of a slightly distorted, nonplanar (fold angle = 18.9 degrees ) rectangle with Sn-Sn distances of 2.8054(6), 2.8111(6), 2.9122(6), and 2.9146(6) ?. The pentane molecules were disordered. Selected mono- and dihalogermanes were treated with 1 equiv of Li(THF)(3)Si(SiMe(3))(3) or Li(THF)(2.5)Ge(SiMe(3))(3), affording (Me(3)Si)(3)EGe(CF(3))(3) (E = Si, Ge) and (Me(3)Si)(3)GeGeR(3) (R = Cl, CH(3), C(6)H(5)). Besides the monosubstitution product, the reaction of GeCl(4) with 1 equiv of Li(THF)(2.5)Ge(SiMe(3))(3) also gave a small amount of the linear tetragermane (Me(3)Si)(3)GeGeCl(2)GeCl(2)Ge(SiMe(3))(3). Good yields of the analogous phenyl derivative, (Me(3)Si)(3)GeGePh(2)GePh(2)Ge(SiMe(3))(3), were obtained by treating Ph(2)GeCl(2) with 2 equiv of the lithium-germyl reagent.     

含Mo-Ge,W-Ge键的双金属和三金属化合物的合成

本文报导了含钼-锗键, 钨-锗键的双金属化合物的一种有效的合成方法: 和用二氯锗烯二氧六环络合物为原料, 通过对金属──卤素键的插入反应合成金属─金属键。本文合成的化合物经C,H,Cl元素分析, IR, ^1H NMR, MS证实了它们的组成和结构。