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1.
We report on the synthesis of new derivatives of silylated clusters of the type [Ge9(SiR3)3]? (R = SiMe3, Me = CH3; R = Ph, Ph = C6H5) as well as on their reactivity towards copper and zinc compounds. The silylated cluster compounds were synthesized by heterogeneous reactions starting from the Zintl phase K4Ge9. Reaction of K[Ge9{Si(SiMe3)3}3] with ZnCl2 leads to the already known dimeric compound [Zn(Ge9{Si(SiMe3)3}3)2] ( 1 ), whereas upon the reaction with [ZnCp*2] the coordination of [ZnCp*]+ to the cluster takes place (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl) under the formation of [ZnCp*(Ge9{Si(SiMe3)3}3)] ( 2 ). A similar reaction leads to [CuPiPr3(Ge9{Si(SiMe3)3}3)] ( 3 ) from [CuPiPr3Cl] (iPr=isopropyl). Further we investigated the novel silylated cluster units [Ge9(SiPh3)3]? ( 4 ) and [Ge9(SiPh3)2]? ( 5 ), which could be identified by mass spectroscopy. Bis‐ and tris‐silylated species can be synthesized by the respective stoichiometric reactions, and the products were characterized by ESI‐MS and NMR experiments. These clusters show rather different reactivity. The reaction of the tris‐silylated anion 4 with [CuPiPr3Cl] leads to [(CuPiPr3)3Ge9(SiPh3)2]+ as shown from NMR experiments and to [(CuPiPr3)4{Ge9(SiPh3)2}2] ( 6 ), which was characterized by single‐crystal X‐ray diffraction. Compound 6 shows a new type of coordination of the Cu atoms to the silylated Zintl clusters.  相似文献   

2.
Ga2Br2R2 and Ga3I2R3 [R = C(SiMe3)3] — Two New Organoelement Subhalides of Gallium Containing One or Two Ga‐Ga Single Bonds The oxidation of the tetrahedral tetragallium cluster Ga4[C(SiMe3)3]4 ( 1 ) with elemental bromine in the presence of AlBr3 yielded the corresponding gallium subhalide Ga2Br2R2 [ 4 , R = C(SiMe3)3], which remains monomer even in the solid state and in which the GaII atoms are connected by a short Ga‐Ga single bond [243.2(2) pm]. The analogous diiodide Ga2I2R2 ( 3 ), which was obtained on a similar route by our group only recently, did not react with lithium tert‐butanolate by substitution as originally expected. Instead, partial disproportionation occurred with the formation of the trigallium diiodide Ga3I2R3 ( 6 ), in which three Ga atoms are connected by two Ga‐Ga single bonds (255.1 pm on average). Both terminal Ga atoms have a coordination number of four owing to the bridging function of both iodine atoms, while the inner one which has an oxidation number of +1 remains coordinatively unsaturated. An average oxidation state of 1.66 resulted for all atoms of the chain. The GaIII compound {[GaI(R)(OCMe3)(OH)]Li}2 ( 7 ) was isolated as the second product of the disproportionation. It is a dimer in the solid state via Li‐O bridges and shows a hindered rotation of its tert‐butyl group.  相似文献   

3.
Synthesis, NMR Spectra and Structure of [(CH3)2Ga{μ‐P(H)Si(CH3)3}2Ga(CH3)2{μ‐P(Si(CH3)3)2}Ga(CH3)2] The title compound has been prepared in good yield by the reaction of [Me2GaOMe]3 (Me = CH3) with HP(SiMe3)2 in toluene (ratio 1 : 1,1) and purified by crystallization from pentane or toluene, respectively. This organogallium compound forms (Ga–P)3 ring skeletons with one Ga–P(SiMe3)2–Ga and two Ga–P(H)SiMe3–Ga bridges and crystallizes in the monoclinic space group C2/c. The known homologous Al‐compound is isotypic, both (MIII–P)3 heterocycles have twist‐conformations, the ligands of the monophosphane bridges have trans arrangements.  相似文献   

4.
A “naked” aluminum atom links two aluminum tetrahedra in the [Al7{N(SiMe3)2}6]− ion (see picture), which results from the reaction of a metastable AlCl solution with LiN(SiMe3)2 and crystallizes with [Li(OEt2)3]+ as cation. This unique structure among molecular metal atom clusters represents a small but characteristic section of cubic close-packed aluminum.  相似文献   

5.
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXII. The Formation of [η2‐{tBu–P=P–SiMe3}Pt(PR3)2] from (Me3Si)tBuP–P=P(Me)tBu2 and [η2‐{C2H4}Pt(PR3)2] (Me3Si)tBuP–P = P(Me)tBu2 reacts with [η2‐{C2H4}Pt(PR3)2] yielding [η2‐{tBu–P=P–SiMe3}Pt(PR3)2]. However, there is no indication for an isomer which would be the analogue to the well known [η2‐{tBu2P–P}Pt(PPh3)2]. The syntheses and NMR data of [η2‐{tBu–P=P–SiMe3}Pt(PPh3)2] and [η2‐{tBu–P=P–SiMe3}Pt(PMe3)2] as well as the results of the single crystal structure determination of [η2‐{tBu–P=P–SiMe3}Pt(PPh3)2] are reported.  相似文献   

6.
The reaction of CuCl, LiAs(SiMe3)2 and dppb (Bis(diphenylphosphino)butane) leads to the formation of ionic cluster complexes. Depending on the reaction conditions one can isolate [Cu8As3(AsSiMe3)2(dppb)4]+[Cu{As2(SiMe3)2}{As4(SiMe3)4}]‐ ( 1 ) and [Cu8As3(AsSiMe3)2(dppb)4]+[Cu{As(SiMe3)2}2]‐ ( 2 ). The same reaction of CuCl, dppm (Bis(diphenylphosphino)methane) and LiSb(SiMe3)2 leads to the neutral cluster complex [Cu10(Sb3)2(SbSiMe3)2(dppm)6] ( 3 ). The structures of 1‐3 have been solved by X‐ray single crystal analyses.  相似文献   

7.
The reaction of [(ArN)2MoCl2] · DME (Ar = 2,6‐i‐Pr2C6H3) ( 1 ) with lithium amidinates or guanidinates resulted in molybdenum(VI) complexes [(ArN)2MoCl{N(R1)C(R2)N(R1)}] (R1 = Cy (cyclohexyl), R2 = Me ( 2 ); R1 = Cy, R2 = N(i‐Pr)2 ( 3 ); R1 = Cy, R2 = N(SiMe3)2 ( 4 ); R1 = SiMe3, R2 = C6H5 ( 5 )) with five coordinated molybdenum atoms. Methylation of these compounds was exemplified by the reactions of 2 and 3 with MeLi affording the corresponding methylates [(ArN)2MoMe{N(R1)C(R2)N(R1)}] (R1 = Cy, R2 = Me ( 6 ); R1 = Cy, R2 = N(i‐Pr)2 ( 7 )). The analogous reaction of 1 with bulky [N(SiMe3)C(C6H5)C(SiMe3)2]Li · THF did not give the corresponding metathesis product, but a Schiff base adduct [(ArN)2MoCl2] · [NH=C(C6H5)CH(SiMe3)2] ( 8 ) in low yield. The molecular structures of 7 and 8 are established by the X‐ray single crystal structural analysis.  相似文献   

8.
The asymmetric unit of the title compound, dipotassium bis[hexaaquanickel(II)] tris(μ2‐methylenediphosphonato)tripalladium(II) hexahydrate, K2[Ni(H2O)6]2[Pd3{CH2(PO3)2}3]·6H2O, consists of half a {[Pd{CH2(PO3)2}]3}6− anion [one Pd atom (4e) and a methylene C atom (4e) occupy positions on a twofold axis] in a rare `handbell‐like' arrangement, with K+ and [Ni(H2O)6]2+ cations to form the neutral complex, completed by three solvent water molecules. The {[Pd{CH2(PO3)2}]3}6− units exhibit close Pd...Pd separations of 3.0469 (4) Å and are packed via intermolecular C—H...Pd hydrogen bonds. The [KO9] and [NiO6] units are assembled into sheets coplanar with (011) and stacked along the [100] direction. Within these sheets there are [K4Ni4O8] and [K2Ni2O4] loops. Successive alternation of the sheets and [Pd{CH2(PO3)2}]3 units parallel to [001] produces the three‐dimensional packing, which is also supported by a dense network of hydrogen bonds involving the solvent water molecules.  相似文献   

9.
First‐row two‐coordinate complexes are attracting much interest. Herein, we report the high‐yield isolation of the linear two‐coordinate iron(I) complex salt [K(L)][Fe{N(SiMe3)2}2] (L=18‐crown‐6 or crypt‐222) through the reduction of either [Fe{N(SiMe3)2}2] or its three‐coordinate phosphine adduct [Fe{N(SiMe3)2}2(PCy3)]. Detailed characterization is gained through X‐ray diffraction, variable‐temperature NMR spectroscopy, and magnetic susceptibility studies. One‐ and two‐electron oxidation through reaction with I2 is further found to afford the corresponding iodo iron(II) and diiodo iron(III) complexes.  相似文献   

10.
First‐row two‐coordinate complexes are attracting much interest. Herein, we report the high‐yield isolation of the linear two‐coordinate iron(I) complex salt [K(L)][Fe{N(SiMe3)2}2] (L=18‐crown‐6 or crypt‐222) through the reduction of either [Fe{N(SiMe3)2}2] or its three‐coordinate phosphine adduct [Fe{N(SiMe3)2}2(PCy3)]. Detailed characterization is gained through X‐ray diffraction, variable‐temperature NMR spectroscopy, and magnetic susceptibility studies. One‐ and two‐electron oxidation through reaction with I2 is further found to afford the corresponding iodo iron(II) and diiodo iron(III) complexes.  相似文献   

11.
Novel silylation reactions at [Ge9] Zintl clusters starting from the chlorosilanes SiR3Cl (R = iBu, iPr, Et) and the Zintl phase K4Ge9 are reported. The formation of the tris‐silylated anions [Ge9(SiR3)3]– [R = iBu ( 1a ), iPr ( 1b ), Et ( 1c )] by heterogeneous reactions in acetonitrile was monitored by ESI‐MS measurements. For R = iBu 1H, 13C and 29Si NMR experiments confirmed the exclusive formation of 1a . Subsequent reactions of 1a with CuNHCDippCl and Au(PPh3)Cl result in formation of the neutral metal complex (CuNHCDipp)[Ge9{Si(iBu)3}3]·0.5 tol ( 2 ·0.5 tol) and the metal bridged dimeric unit {Au[Ge9{Si(iBu)3}3]2}– ( 3a ), isolated as a (K‐18c6)+ salt in (K‐18c6)Au[Ge9{Si(iBu)3}3]2·tol ( 3 ·tol), respectively. Finally, from a toluene/hexane solution of 1a in presence of 18‐crown‐6, crystals of the compound (K‐18c6)2[Ge9{Si(iBu)3}2]·tol ( 4 ·tol), containing the bis‐silylated cluster anion [Ge9(Si(iBu)3)2]2– ( 4a ), were obtained. The compounds 2 ·0.5 tol, 3 ·tol and 4 ·tol were characterized by single‐crystal structure determination.  相似文献   

12.
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   

13.
The novel metalloid germanium cluster [Ge9(Hyp)2HypGe]– ( 1 ) was synthesized, exhibiting two different bulky groups [Hyp = Si(SiMe3)3; HypGe = Ge(SiMe3)3]. Further reaction of 1 with ZnCl2 gives the derivative [ZnGe18(Hyp)4(HypGe)2] ( 2 ) in good yield, showing that the substitution of Si(SiMe3)3 by Ge(SiMe3)3 within a metalloid Ge9R3– compound leads to a comparable reactivity. 1 and 2 are characterized by NMR spectroscopy, mass spectrometry ( 1 ) and single crystal structure analyses ( 2 ). 1 and 2 are the first metalloid germanium clusters bearing germyl groups.  相似文献   

14.
Single crystals of [Be3(μ3‐O)3(MeCN)6{Be(MeCN)3}3](I)6·4CH3CN ( 1 ·4CH3CN) were obtained in low yield by the reaction of beryllium powder with iodine in acetonitrile suspension, which probably result from traces of beryllium oxide containing the applied beryllium metal. The compound 1 ·4CH3CN forms moisture sensitive, colourless crystal needles, which were characterized by IR spectroscopy and X‐ray diffraction (Space group Pnma, Z = 4, lattice dimensions at 100(2) K: a = 2317.4(1), b = 2491.4(1), c = 1190.6(1) pm, R1 = 0.0315). The hexaiodide complex cation 1 6+consists of a cyclo‐Be3O3 core with slightly distorted chair conformation, stabilized by coordination of two acetonitrile ligands at each of the beryllium atoms and by a {Be(CH3CN)3}2+ cation at each of the oxygen atoms. This unique coordination behaviour results in coplanar OBe3 units with short Be–O distances of 155.0 pm and 153.6 pm on average of bond lengths within the cyclo‐Be3O3 unit and of the peripheric BeO bonds, respectively. Exposure of compound 1 ·4CH3CN to moist air leads to small orange crystal plates of [Be(H2O)4]I2·2CH3CN ( 3 ·2CH3CN). According to the crystal structure determination (Space group C2/c, Z = 4, lattice dimensions at 100(2) K: a = 1220.7(1), b = 735.0(1), c = 1608.5(1) pm, β = 97.97(1)°, R1 = 0.0394), all hydrogen atoms of the dication [Be(H2O)4]2+ are involved to form O–H ··· N and O–H ··· I hydrogen bonds with the acetonitrile molecules and the iodide ions, respectively. Quantum chemical calculations (B3LYP/6‐311+G**) at the model [Be3(μ3‐O)3(HCN)6{Be(HCN)3}3]6+ show that chair and boat conformation are stable and that the distorted chair conformation is stabilized by packing effects.  相似文献   

15.
The reaction of the organolithium derivative {2, 6‐[P(O)(OEt)2]2‐4‐tert‐Bu‐C6H2}Li ( 1 ‐Li) with [Ph3C]+[PF6]— gave the substituted biphenyl derivative 4‐[(C6H5)2CH]‐4′‐[tert‐Bu]‐2′, 6′‐[P(O)(OEt)2]2‐1, 1′‐biphenyl ( 5 ) which was characterized by 1H, 13C and 31P NMR spectroscopy and single crystal X‐ray analysis. Ab initio MO‐calculations reveal the intramolecular O···C distances in 5 of 2.952(4) and 2.988(5)Å being shorter than the sum of the van der Waals radii of oxygen and carbon to be the result of crystal packing effects. Also reported are the synthesis and structure of the bromine‐substituted derivative {2, 6‐[P(O)(OEt)2]2‐4‐tert‐Bu]C6H2}Br ( 9 ) and the structure of the protonated ligand 5‐tert‐Bu‐1, 3‐[P(O)(OEt)2]2C6H3 ( 1 ‐H). The structures of 1 ‐H, 5 , and 9 are compared with those of related metal‐substituted derivatives.  相似文献   

16.
Synthesis, Crystal Structure, Electronic Structure, Spectroscopic and Magnetic Properties of [VOCl2{P(SiMe3)3}2]: A Phosphane Complex with a Disordered VOCl2 Group VOCl3 reacts with P(SiMe3)3 to form blue green crystals of [VOCl2{P(SiMe3)3}2] ( 1 ). The X-ray crystal structure analysis of 1 (cubic space group P213: a = 1541.4(1) pm, Z = 4) reveals a slightly distorded trigonal bipyramidal coordination environment for the disordered vanadium(IV) center. Density functional calculations on the compound [VOCl2{P(SiH3)3}2] ( 2 ) are in accord with this observation. 1 has been characterized by ESR, vibrational (IR and Raman) and electronic absorption spectroscopy and magnetic measurements. The ESR spectra of 1 in a toluene solution (293 K and frozen solution at 6 K) exhibit hyperfine interactions of the unpaired electron with the 51V center (I = 7/2) and the 31P centers (I = 1/2) of the two equivalent phosphane ligands. The ligand-field transitions of the VOCl2{P}2 chromophore observed in the electronic absorption spectrum have been assigned on the basis of density functional calculations on 2 .  相似文献   

17.
Trialkylhydridoalanates RxR′3?xAlH? [R = CMe3; R′ = CH(SiMe3)2] The very strong base tert-butyl lithium reacts in the presence of chelating tetramethylethylendiamine with the aluminium organyls Al[CH(SiMe3)2]2CMe3 1 and Al[CH(SiMe3)2](CMe3)2 2 not under proton abstraction from the C? H acidic elementorganic substituent, but under β-elimination and addition of the thereby formed LiH to the coordinatively unsaturated aluminium atom. Two alanates — [Hal{CH(SiMe3)2}2CMe3]? 3 and [HAl{CH(SiMe3)2}(CMe3)2]? 4 each with Li(TMEDA)2⊕ as counterion — were isolated; they exhibit separate anions and cations in solid state as shown by a crystal structure determination on 3 . In absence of the chelating amine tert-butyl lithium decomposes under the catalytic effect of the aluminium compound to LiH, which does not add to aluminium and precipitates in a reactive form.  相似文献   

18.
The reduction of the tribromoamidosilane {N(SiMe3)Dipp}SiBr3 (Dipp=2,6‐i Pr2C6H3) with potassium graphite or magnesium resulted in the formation of [Si4{N(SiMe3)Dipp}4] ( 1 ), a bicyclo[1.1.0]tetrasilatetraamide. The Si4 motif in 1 does not adopt a tetrahedral substructure and exhibits two three‐coordinate and two four‐coordinate silicon atoms. The electronic situation on the three‐coordinate silicon atoms is rationalized with positive and negative polarization based on EPR analysis, magnetization measurements, and DFT calculations as well as 29Si CP MAS NMR and multinuclear NMR spectroscopy in solution. Reactivity studies with 1 and radical scavengers confirmed the partial charge separation. Compound 1 reacts with sulfur to give a novel type of silicon sulfur cage compound substituted with an amido ligand, [Si4S3{N(SiMe3)Dipp}4] ( 2 ).  相似文献   

19.
By reacting Mn2(CO)10 and TeI4 in the ionic liquid[BMIm][OTf] (1‐butyl‐3‐methylimidazolium trifluromethanesulfonate), brick‐red crystals of [BMIm][(Te2)3{Mn(CO)3}2{Mn(CO)4}3]are obtained. The title compound contains the carbonyl anion[(Te2)3{Mn(CO)3}2{Mn(CO)4}3]–. Herein, three formal Te22– units and two formal Mn(CO)3+ fragments establish a distorted heterocubane‐like Te6Mn2 structure. Three edges of this heterocubane are furthermore capped by Mn(CO)4+ fragments. The resulting Te6Mn5 building unit, moreover, looks very similar to the P113– anion – the so‐called ufosane. The mean distances Te–Te and Te–Mn are observed with 277.6 and 264.7 pm, respectively. In addition to single‐crystal structure analysis, the title compound is characterized by infrared spectroscopy (FT‐IR), thermogravimetry (TG) and energy‐dispersive X‐ray (EDX) analysis.  相似文献   

20.
The Reaction of the Digallium Subiodide R(I)Ga‐Ga(I)R [R = C(SiMe3)3] with Lithium Diphenylphosphanide – Radical Cleavage of the Ga‐Ga Bond The easily available organoelement digallium(II) subiodide R(I)Ga‐Ga(I)R ( 1 ) [R = C(SiMe3)3] reacted with two equivalents of lithium diphenylphosphanide in toluene by the replacement of both iodine atoms by two phosphanido groups. The product, [R(H)Ga‐P(C6H5)2]2 ( 2 ), contains a four‐membered Ga2P2 heterocycle without direct Ga‐Ga bonding interactions and the gallium atoms exclusively in an oxidation state of +III. They are attached to hydrogen atoms, which may result from a reaction of a reactive intermediate with the solvent.  相似文献   

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