Komplexchemie P‐reicher Phosphane und Silylphosphane. XXII. Die Bildung von [η2‐{tBu–P=P–SiMe3}Pt(PR3)2]aus (Me3Si)tBuP–P=P(Me)tBu2 und [η2‐{C2H4}Pt(PR3)2]

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.     

Synthese und Metallierungen der tripodalen Siloxazan-Liganden tBuSi(OSiMe2NHR)3 [R = H,Me, tBu,Ph, SiMe3]

Synthesis and Metalation of Tripodal Siloxazane Ligands ^tBuSi(OSiMe₂NHR)₃ [R = H, Me, ^tBu, Ph, SiMe₃] ^tBuSi(OSiMe₂Cl)₃ ( 1 ) was generated by the condensation of tert-butylsilanetriol with dichlorodimethylsilane under elimination of HCl. A series of tripodal amines ^tBuSi(OSiMe₂NHR)₃ [R = H ( 2 ), R = Me ( 3 ), R = ^tBu ( 4 ), R = Ph ( 5 )] was synthesized by ammonolysis, aminolysis or salt elimination of 1 with primary lithium amides. 5  has been subjected to single crystal X-ray diffraction, which confirmed the triarmed amine. The siloxamine ^tBuSi(OSiMe₂NHSiMe₃)₃ ( 6 ) was generated by the reaction of 2 with three moles of chlorotrimethylsilane. The lithium amides ^tBuSi(OSiMe₂N[Li]^tBu)₃ ( 7 ), ^tBuSi(OSiMe₂N[Li]Ph)₃ ( 8 ) and ^tBuSi(OSiMe₂N[Li]SiMe₃)₃ ( 11 ) and the sodium amide ^tBuSi(OSiMe₂N[Na]^tBu)₃ ( 9 ) were obtained by the complete hydrogen–metal exchange of the amines 4 – 6 with n-butyl lithium and n-butyl sodium in hexane, respectively. The transmetalation of 7 with copper(I) chloride gave the copper amide ^tBuSi(OSiMe₂N[Cu]^tBu)₃ ( 10 ). The single crystal X-ray diffraction of the metal amides 7 , 9 and 11 shows a trifold coordination by additional interactions between each of the two metal atoms with oxygens in the siloxane groups in contrast to the copper amide 10 , which lacks such contacts. The almost isostructural metal amides 7 , 9 – 11 are monomeric and possess, similary to 5 , a pseudo three fold symmetry in the solid state. 5 and 7 crystallize in the monoclinic space group P2₁/c whereas the compounds 9 – 11 crystallize in the centrosymmetric triclinic space group P 1.     

[Co(g5‐Me5C5)(g3‐tBu2PPCH–CH3)] aus [Co(g5‐Me5C5)(g2‐C2H4)2] und tBu2P–P=P(Me)tBu2

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XVII [1] [Co(g⁵‐Me₅C₅)(g³‐^tBu₂PPCH–CH₃)] from [Co(g⁵‐Me₅C₅)(g²‐C₂H₄)₂] and ^tBu₂P–P=P(Me)^tBu₂ [Co(η⁵‐Me₅C₅)(η³‐^tBu₂PPCH–CH₃)] 1 is formed in the reaction of [Co(η⁵‐Me₅C₅)(η²‐C₂H₄)₂] 2 with ^tBu₂P–P 4 (generated from ^tBu₂P–P=P(Me)^tBu₂ 3 ) by elimination of one C₂H₄ ligand and coupling of the phosphinophosphinidene with the second one. The structure of 1 is proven by ³¹P, ¹³C, ¹H NMR spectra and the X‐ray structure analysis. Within the ligand ^tBu₂P¹P²C¹H–CH₃ in 1 , the angle P1–P2–C1 amounts to 90°. The Co, P1, P2, C1 atoms in 1 look like a „butterfly”︁. The reaction of 2 with a mixture of ^tBu₂P–P=P(Me)^tBu₂ 3 and ^tBu–C?P 5 yields [Co(η⁵‐Me₅C₅){η⁴‐(^tBuCP)₂}] 6 and 1 . While 6 is spontaneously formed, 1 appears only after complete consumption of 5 .     

Synthesis and Structure of (N,)C,N‐chelated Organoantimony(III) and Bismuth(III) Cations and Isolation of Their Adducts with Ag[CB11H12]

The treatment of N,C,N‐chelated antimony(III) and bismuth(III) chlorides [C₆H₃‐2,6‐(CH=NR)₂]MCl₂ [R = tBu and M = Sb ( 1 ) or Bi ( 2 ); R = Dmp and M = Sb ( 3 ) or Bi ( 4 )] (Dmp = 2,6‐Me₂C₆H₃) with one molar equivalent of Ag[CB₁₁H₁₂] led to a smooth formation of corresponding ionic pairs {[C₆H₃‐2,6‐(CH=NR)₂]MCl}⁺[CB₁₁H₁₂]^– [R = tBu and M = Sb ( 7 ) or Bi ( 8 ), R = Dmp and M = Sb ( 9 ) or Bi ( 10 )]. Similarly, the reaction of C,N‐chelated analogues [C₆H₂‐2‐(CH=NDip)‐4,6‐(tBu)₂]MCl₂ [M = Sb ( 5 ) or Bi ( 6 ), Dip = 2′,6′‐iPr₂C₆H₃] gave compounds {[C₆H₂‐2‐(CH=NDip)‐4,6‐(tBu)₂]MCl}⁺[CB₁₁H₁₂]^– [M = Sb ( 11 ) or Bi ( 12 )]. All compounds 7 – 12 were characterized with ¹H, ¹¹B and ¹³C{¹H} NMR spectroscopy, ESI‐mass spectrometry, IR spectroscopy, and molecular structures of 7 – 9 and 12 were determined by the help of single‐crystal X‐ray diffraction analysis. In contrast, all attempts to cleave also the second M–Cl bond in 7 – 12 using another molar equivalent Ag[CB₁₁H₁₂] remained unsuccessful. Nevertheless, the reaction between 7 (or 8 ) and Ag[CB₁₁H₁₂] produced unprecedented adducts of both reagents namely {[C₆H₃‐2,6‐(CH=NtBu)₂]SbCl}₂²⁺[Ag₂(CB₁₁H₁₂)₄]^2– ( 13 ) and {[C₆H₃‐2,6‐(CH=NtBu)₂]BiCl}⁺[Ag(CB₁₁H₁₂)₂]^– ( 14 ) in a reproducible manner. The molecular structures of these sparingly soluble compounds were determined by single‐crystal X‐ray diffraction analysis.     

Synthesis and Structural Characterization of Some Novel Trialkylsilyl‐substituted Lithium Benzyl Complexes [Li(tmeda)][CHRSiMe2R′] (R = Ph, 3,5‐Me2C6H3; R′ = Me,tBu, Ph)

The reactions of PhCH₂SiMe₃ ( 1 ), PhCH₂SiMe₂^tBu ( 2 ), PhCH₂SiMe₂Ph ( 3 ), 3,5‐Me₂C₆H₃CH₂SiMe₃ ( 4 ), and 3,5‐Me₂C₆H₃CH₂SiMe₂^tBu ( 5 ) with ⁿBuLi in tetramethylethylenediamine (tmeda) afford the corresponding lithium complexes [Li(tmeda)][CHRSiMe₂R′] (R, R′ = Ph, Me ( 6 ), Ph, ^tBu ( 7 ), Ph, Ph ( 8 ), 3,5‐Me₂C₆H₃, Me ( 9 ), and 3,5‐Me₂C₆H₃, ^tBu ( 10 )), respectively. The new compounds 5 , 7 , 8 , 9 and 10 have been characterized by ¹H and ¹³C NMR spectroscopy, compounds 7 , 8 and 9 also by X‐ray structure analysis.     

Schrittweise Darstellung von verzweigten tripodalen Chlor‐Methyl‐Siloxanen der allgemeinen Formel tBuSi[{OSiMe2}yOSiMe3–xClx]3 [x = 0–3; y = 0–2] sowie Synthese der Silanole tBuSi[(OSiMe2)xOH]3 [x = 1, 2] und des bicyclischen Siloxans tBuSi(OSiMe2O)3SitBu

The branched tripodal chloro‐methyl‐siloxanes of the general formula tBuSi[{OSiMe₂}_yOSiMe_3–xCl_x]₃ [x = 0–3; y = 0–2] were synthesized, starting with tert‐Butyl‐trisilanol ( 1 ). The treatment of 1 with the chloro‐methyl‐silanes (Me_3–xSiCl_x+1) (x = 0–3) in the presence of triethylamine leads to the compounds tBuSi(OSiMe₂Cl)₃ ( 2 ), tBuSi(OSiMeCl₂)₃ ( 3 ) and tBuSi(OSiCl₃)₃ ( 4 ). The siloxanes 2 – 4 are colourless oily liquids, which can be purified by distillation. Their yields decrease with the number of chloro substituents. In the reaction of compound 2 with three equivalents of water the silantriol tBuSi(OSiMe₂OH)₃ ( 5 ) is generated which is used to create the branched tripodal chloro‐methyl‐siloxanes tBuSi(OSiMe₂OSiMe₃)₃ ( 6 ), tBuSi(OSiMe₂OSiMe₂Cl)₃ ( 7 ), tBuSi(OSiMe₂OSiMeCl₂)₃ ( 9 ) and tBuSi(OSiMe₂OSiCl₃)₃ ( 10 ). Compound ( 7 ) is only a side product with a yield of 25 %., The cyclic tBuSi[{(OSiMe₂)₂Cl}(OSiMe₂)₃O] ( 8 ) can be isolated and characterised. The transformation of the compound tBuSi(OSiMe₂OSiMe₂Cl)₃ ( 7 ) into the trisilanol tBuSi(OSiMe₂OSiMe₂OH)₃ ( 11 ) allows to prepare the tripodale siloxane tBuSi(OSiMe₂OSiMe₂OSiMe₃)₃ ( 12 ) in good yields., The reaction of tBuSi(OSiMe₂Cl)₃ ( 2 ) with tert‐butyl trisilanol 1 leads to the formation of bicyclic tBuSi(OSiMe₂O)₃SitBu ( 13 ). An X‐ray structure determination on 13 reveals a [3.3.3]‐bicycle with a C₃ axis, which crystallizes in the cubic crystal system in the space group Pa . The reported compounds 2 – 13 were characterised by NMR‐ and IR spectroscopy ( 5 , 11 ) and show correct elemental analyses. The ²⁹Si‐NMR‐data of the compounds show interesting trends with respect to the Si–O chain length and the chloro substistuents.     

Neue amido‐ und imidoverbrückte Kupferkomplexe – Synthesen und Strukturen von [{Li(OEt2)}2][Cu(NPh2)3], [ClCuN(SnMe3)3], [{CuN(SnMe3)2}4], [Cu16(NH2tBu)12Cl16], [{CuNHtBu}8], [Li(dme)3][Cu6(NHMes)3(NMes)2], [PPh3(C6H4)CuNHMes], [{[Li(dme)][Cu(NHMes)(NHPh)]}2] und [{Li(dme)3}3][Li(dme)2][Cu12(NPh)8]

New Amido and Imido Bridged Complexes of Copper – Syntheses and Structures of [{Li(OEt₂)}₂][Cu(NPh₂)₃], [ClCuN(SnMe₃)₃], [{CuN(SnMe₃)₂}₄], [Cu₁₆(NH₂^tBu)₁₂Cl₁₆], [{CuNH^tBu}₈], [Li(dme)₃][Cu₆(NHMes)₃(NMes)₂], [PPh₃(C₆H₄)CuNHMes], [{[Li(dme)][Cu(NHMes)(NHPh)]}₂], and [{Li(dme)₃}₃][Li(dme)₂][Cu₁₂(NPh)₈] The reactions of stannylated and lithiated amines with coppersalts (halogenides, thiocyanates) lead to amido and imido bridged complexes which contain one to twelve metal atoms. [{Li(OEt₂)}₂][Cu(NPh₂)₃] ( 1 ) results from the reaction of CuCl with LiNPh₂ in the presence of trimethylphosphine. With N(SnMe₃)₃, CuCl reacts to the donor‐acceptor complex [ClCuN(SnMe₃)₃] ( 2 ) that is transformed into the tetrameric complex [{CuN(SnMe₃)₂}₄] ( 3 ) by thermolysis. 3 can also be obtained by the reaction of LiN(SnMe₃)₂ with Cu(SCN)₂. While terminally bound in 1 , the amido ligand is μ₂‐bridging between copper atoms in compound 3 . The influence of the alkyl amide's leaving group can be seen from a comparison of the reactivity of Me₃SnNH^tBu and LiNH^tBu, respectively. With Me₃SnNH^tBu, CuCl₂ forms the polymeric compound [Cu₁₆(NH₂^tBu)₁₂Cl₁₆] ( 4 ) whereas in the case of LiNH^tBu with both CuCl and CuSCN, the complex [{CuNH^tBu}₈] ( 5 ) is obtained. The latter contains two planar Cu₄N₄‐rings similar to those in 3 . If a mesityl group is introduced at the lithium amide, different products are accessible. Both, CuBr and CuSCN, lead to the formation of [Li(dme)₃][Cu₆(NHMes)₃(NMes)₂] ( 6 ) whose anion consists of a prismatic copper core with μ₂‐bridging amido and μ₃‐bridging imido ligands. In the presence of PPh₄Cl, a mixture of Cu(SCN)₂ and LiNHMes enables an ortho‐metallation reaction that produces [PPh₃(C₆H₄)CuNHMes] ( 7 ). From the reaction of CuSCN with LiNHMes and LiNHPh either the dimeric complex [{[Li(dme)][Cu(NHMes)(NHPh)]}₂] ( 8 ) or the cluster [{Li(dme)₃}₃][Li(dme)₂][Cu₁₂(NPh)₈] ( 9 ) results. The anion in 9 exhibits a cubo‐octahedron of copper atoms μ₃‐bridged by (NPh)^2–‐ligands. The solid state structures of compounds 1 – 9 have been determined by single crystal X‐ray diffraction.     

Synthesis and Structure of a Novel Cluster with Trigonal-bipyramidal Ge_2Ru_3 Core

ＩｎｔｒｏｄｕｃｔｉｏｎＷｅｒｅｃｅｎｔｌｙｒｅｐｏｒｔｅｄａｎｉｎｔｒａｍｏｌｅｃｕｌａｒｔｈｅｒｍａｌｒｅａｒ ｒａｎｇｅｍｅｎｔｂｅｔｗｅｅｎＳｉ—ＳｉａｎｄＦｅ—Ｆｅｂｏｎｄｓｉｎｔｈｅｄｉｎｕ ｃｌｅａｒｉｒｏｎｃｏｍｐｌｅｘ { (Ｍｅ2 ＳｉＳｉＭｅ2 ) [(η5 Ｃ5Ｈ4 )Ｆｅ(ＣＯ) ]2 (μ ＣＯ) 2 } (Ｓｃｈｅｍｅ 1) .1 5Ｔｈｅｔｈｅｒｍａｌｒｅａｒｒａｎｇｅｍｅｎｔｗａｓｌａｔｅｒｅｘｔｅｎｄｅｄｔｏｇｅｒｍａｎｉｕｍ ｉｒｏｎａｎｄｓｉｌｉｃｏｎ ｒｕｔｈｅｎｉ ｕｍａｎａｌｏｇｕｅｓ .6 8Ｔｈ…     

Neue mehrkernige Indium–Stickstoff‐Verbindungen – Synthese und Kristallstrukturen von [In4X4(NtBu)4] (X = Cl,Br, I) und [In3Br4(NtBu)(NHtBu)3]

New Polynuclear Indium Nitrogen Compounds – Synthesis and Crystal Structures of [In₄X₄(N^tBu)₄] (X = Cl, Br, I) and [In₃Br₄(N^tBu)(NH^tBu)₃] The reaction of the indium trihalides InX₃ (X = Cl, Br, I) with LiNH^tBu in THF leads to the In₄N₄‐heterocubanes [In₄X₄(N^tBu)₄] (X = Cl 1 , Br 2 , I 3 ). Additionally [In₃Br₄(N^tBu)(NH^tBu)₃] ( 4 ) was obtained as a by‐product in the synthesis of 2 . 1 – 4 have been characterized by x‐ray crystal structure analysis. 1 – 3 consist of In₄N₄ heterocubane cores with an alternating arrangement of In and N atoms. The In atoms are coordinated nearly tetrahedrally by three N‐atoms and a terminal halogen atom. 4 contains a tricyclic In₃N₄ core which can be formally derived from an In₄N₄‐heterocubane by removing one In atom.     

[p‐tBu‐calix[4](OMe)2(OBeCl)2]: The First Structually Characterized Beryllium Calixarene Complex

Treatment of [p‐^tBu‐calix[4](OMe)₂(OLi)₂] with two equivalents of BeCl₂ gave the unprecedented dinuclear beryllium complex [p‐p‐^tBu‐calix[4](OMe)₂(OBeCl)₂], which was structurally characterized, both in solution (NMR) and in the solid state (X‐ray structure analysis).     

Synthese und Struktur von Vanadium(III)- und Vanadium(IV)-silanolaten

Synthesis and Structures of Vanadium(III) and Vanadium(IV) Silanolates The syntheses of the new and partially known vanadium(III)-silanolate complexes [{V(OSiMe^t₂Bu)₃}₂(THF)] ( 1 ), [Li(THF)₂V(OSiMe^t₂Bu)₄] ( 2 ), [V(OSiMe^t₂Bu)(lut)] ( 3 ), V(OSiPh₃)₃(THF)₃ ( 4 ), [Li(THF)₄][V(OSiPh₃)₄](THF)₂ ( 5 ), [Li(DME)VMes(OSiMe^t₂Bu)₃] ( 7 ), [Li(THF)₄][VMes · (OSiPh₃)₃] ( 8 ), [Li(THF)₄][VMes₃(OSiMe^t₂Bu)] ( 9 ), and Na[VMes₃(OSiPh₃)](THF)₄ ( 10 ) as well as the vanadium(IV) compounds [V(OSiPh₃)₄] ( 6 ), [VMes₃(OSiMe^t₂Bu)] ( 11 ) and [VMes₃(OSiPh₃)] ( 12 ) are reported. In most cases the vanadium atom displays a coordination number of four. The dimeric structure of 1 with coordination numbers of four and five, respectively, has been deduced from molecular mass measurements, mass spectrometry and its magnetic properties. The crystal structures of compounds 2 , 4 , 5 , 9 and 11 were resolved. Complex 2 resembles a bridged contact ion pair in which both metal centres are in a tetrahedral coordination environment. In 4 the ligands are arranged trigonal bipyramidally with the THF molecules in the axial positions. Complexes 5 and 9 crystallize in separated ion paires with the vanadium in a tetrahedral coordination sphere. The crystal structure of 11 is analogous to that of 9 but with consequences due to the higher oxidation state. Oxidation of the vanadates(III), e. g. 5 , 9 and 10 , yields the corresponding vanadium(IV) compounds 6 , 11 and 12 .     

Synthese und Kristallstruktur des Kalium‐Iminophosphanids [K4(THF)3(Me3SiNPEt2)2(OSiMe2OSiMe2O)]2

The potassium iminophosphanide complex [K₄(thf)₃(Me₃SiNPEt₂)₂(OSiMe₂OSiMe₂O)]₂ has been obtained by a melt reaction of Me₃SiNPEt₃ with potassium hydride at 140 °C in the presence of silicon grease (—OSiMe₂—)_n and subsequent crystallization from thf solution. The colourless moisture sensitive single crystals are characterized by X‐ray diffraction: Space group P1¯, Z = 1, lattice dimensions at —70 °C: a = 1135.9(3), b = 1250.0(3), c = 1866.1(4) pm, α = 92.65(1)°, β = 100.80(1)°, γ = 93.57(1)°, R₁ = 0.0604. The centrosymmetric dimeric cluster aggregate is formed by two of the eight potassium ions which are connected with the central oxygen atom of both the (OSiMe₂OSiMe₂O)^2— chains as well as with one of their terminal O atoms each. The remaining potassium ions are connected with the phosphorus atoms of the iminophosphanide groups (Me₃SiNPEt₂)^— as well as with its nitrogen atoms. They are terminally solvated by thf molecules.     

Synthese und Kristallstruktur von iso‐Butylimidogalliummethyl, [CH3Ga–NCH2CH(CH3)2]6

Synthesis and X‐Ray Structure Determination of iso ‐Butylimido Galliummethyl, [CH₃Ga–NCH₂CH(CH₃)₂]₆ The thermal decomposition of [Me₂Ga–N(ⁱBu)SnMe₃]₂ (prepared by the reaction of [Me₂SnNⁱBu]₃ with GaMe₃ in a 1:3 molar ratio) in an evacuated, sealed tube at 160°C forms [MeGaNⁱBu]₆ in high yield and SnMe₄. Mass, ¹H and ¹³C NMR as well as some IR and Raman spectroscopic data are given and the crystal structure of this cage molecule with a hexagonal prismatic Ga₆N₆ skeleton has been determined.     

Studien zur Reaktion von [Me2AlP(SiMe3)2]2 mit basenstabilisierten Organogalliumchloriden und ‐hydriden

Investigations on the Reactivity of [Me₂AlP(SiMe₃)₂]₂ with Base‐stabilized Organogalliumhalides and ‐hydrides [Me₂AlP(SiMe₃)₂]₂ ( 1 ) reacts with dmap?Ga(Cl)Me₂, dmap?Ga(Me)Cl₂, dmap?GaCl₃ and dmap?Ga(H)Me₂ with Al‐P bond cleavage and subsequent formation of heterocyclic [Me₂GaP(SiMe₃)₂]₂ ( 2 ) as well as dmap?AlMe_xCl_3?x (x = 3 8 ; 2 3 ; 1 4 ; 0 5 ). The reaction between equimolar amounts of dmap?Al(Me₂)P(SiMe₃)₂ and dmap?Ga(t‐Bu₂)Cl yield dmap?Ga(t‐Bu₂)P(SiMe₃)₂ ( 6 ) and dmap?AlMe₂Cl ( 3 ). 2 – 8 were characterized by NMR spectroscopy, 2 and 6 also by single crystal X‐ray diffraction.     

Über Bildung und Reaktionen der CH2Li‐Derivate von tBu2P–P=P(CH3)tBu2 und (Me3Si)tBuP–P=P(CH3)tBu2

Formation and Reactions of the CH₂Li‐Derivatives of ^tBu₂P–P=P(CH₃)^tBu₂ and (Me₃Si)^tBuP–P=P(CH₃)^tBu₂ With ⁿBuLi, (Me₃Si)^tBuP–P=P(CH₃)^tBu₂ ( 1 ) and ^tBu₂P–P=P(CH₃)^tBu₂ ( 2 ) yield (Me₃Si)^tBuP–P=P(CH₂Li)^tBu₂ ( 3 ) and ^tBu₂P–P=P(CH₂Li)^tBu₂ ( 4 ), wich react with Me₃SiCl to give (Me₃Si)^tBuP–P=P(CH₂–SiMe₃)^tBu₂ ( 5 ) and ^tBu₂P–P=P(CH₂–SiMe₃)^tBu₂ ( 6 ), respectively. With ^tBu₂P–P(SiMe₃)–P^tBuCl ( 7 ), compound 3 forms 5 as well as the cyclic products [H₂C–P(^tBu)₂=P–P(^tBu)–P^tBu] ( 8 ) and [H₂C–P(^tBu)₂=P–P(P^tBu₂)–P(^tBu)] ( 9 ). Also 3 forms 8 with ^tBuPCl₂. The cleavage of the Me₃Si–P‐bond in 1 by means of C₂Cl₆ or N‐bromo‐succinimide yields (Cl)^tBuP–P=P(CH₃)^tBu₂ ( 10 ) or (Br)^tBuP–P=P(CH₃)^tBu₂ ( 11 ), resp. With LiP(SiMe₃)₂, 10 forms (Me₃Si)₂P–P(^tBu)–P=P(CH₃)^tBu₂ ( 12 ), and Et₂P–P(^tBu)–P=P(CH₃)^tBu₂ ( 13 ) with LiPEt₂. All compounds are characterized by ³¹P NMR Data and mass spectra; the ylide 5 and the THF adduct of 4 additionally by X‐ray structure analyses.     

Synthese und Kristallstruktur von [(Me3Si)2BiCu(PMe3)3], dem ersten Komplex mit einer Bismut—Kupfer‐Bindung

Synthesis and Crystal Structure of [(Me₃Si)₂BiCu(PMe₃)₃] — the First Complex with a Bismuth—Copper Bond The reaction of CuO^t Bu with PMe₃ and Bi(SiMe₃)₃ in hexane yields the phosphine‐stabilized complex [(Me₃Si)₂Bi‐Cu( PMe₃)₃]. This synthesis gave rise to the first binuclear Bi—Cu compound to be structurally characterized by X‐ray crystallography.     

Einfluß der Ringatome auf die Struktur von Triel‐Pentel‐Heterozyklen – Synthese und Molekülstrukturen von [Me2InAs(SiMe3)2]2 und [Me2InSb(SiMe3)2]3

Influence of the Ring Atoms on the Structure of Triel‐Pentel Heterocycles – Synthesis and X‐Ray Crystal Structures of [Me₂InAs(SiMe₃)₂]₂ and [Me₂InSb(SiMe₃)₂]₃ Triel‐pentel heterocycles [Me₂InE(SiMe₃)₂]_x have been prepared by dehalosilylation reactions from Me₂InCl and E(SiMe₃)₃ (E = As, x = 2; E = Sb, x = 3) and characterised by NMR spectroscopy and by X‐ray crystal structure analyses. In addition the X‐ray crystal structures of [Me₂GaAs(SiMe₃)₂]₂ and [Me₂InP(SiMe₃)₂]₂ are reported. The compounds complete a family of 13 identically substituted heterocycles [Me₂ME(SiMe₃)₂]_x (M = Al, Ga, In; E = N, P, As, Sb, Bi; x = 2, 3), whose structures were investigated depending on the ring atoms M and E. The tendencies that have been observed concerning the ring sizes can be explained by the interplay of the atomic radii of the central atoms and the sterical demand of the ligands. After a formal separation of the M–E bonds in σ bonds and dative bonds the characteristic differences and trends in the endocyclic and exocyclic bond angles of both centres M and E can be interpreted on the basis of a simple Lewis acid/base adduct model.     

From Dibismuthenes to Three‐ and Two‐Coordinated Bismuthinidenes by Fine Ligand Tuning: Evidence for Aromatic BiC3N Rings through a Combined Experimental and Theoretical Study

The reduction of N,C,N‐chelated bismuth chlorides [C₆H₃‐2,6‐(CH?NR)₂]BiCl₂ [where R=tBu ( 1 ), 2′,6′‐Me₂C₆H₃ ( 2 ), or 4′‐Me₂NC₆H₄ ( 3 )] or N,C‐chelated analogues [C₆H₂‐2‐(CH?N‐2′,6′‐iPr₂C₆H₃)‐4,6‐(tBu)₂]BiCl₂ ( 4 ) and [C₆H₂‐2‐(CH₂NEt₂)‐4,6‐(tBu)₂]BiCl₂ ( 5 ) is reported. Reduction of compounds 1 – 3 gave monomeric N,C,N‐chelated bismuthinidenes [C₆H₃‐2,6‐(CH?NR)₂]Bi [where R=tBu ( 6 ), 2′,6′‐Me₂C₆H₃ ( 7 ) or 4′‐Me₂NC₆H₄ ( 8 )]. Similarly, the reduction of 4 led to the isolation of the compound [C₆H₂‐2‐(CH?N‐2′,6′‐iPr₂C₆H₃)‐4,6‐(tBu)₂]Bi ( 9 ) as an unprecedented two‐coordinated bismuthinidene that has been structurally characterized. In contrast, the dibismuthene {[C₆H₂‐2‐(CH₂NEt₂)‐4,6‐(tBu)₂]Bi}₂ ( 10 ) was obtained by the reduction of 5 . Compounds 6 – 10 were characterized by using ¹H and ¹³C NMR spectroscopy and their structures, except for 7 , were determined with the help of single‐crystal X‐ray diffraction analysis. It is clear that the structure of the reduced products (bismuthinidene versus dibismuthene) is ligand‐dependent and particularly influenced by the strength of the N→Bi intramolecular interaction(s). Therefore, a theoretical survey describing the bonding situation in the studied compounds and related bismuth(I) systems is included. Importantly, we found that the C₃NBi chelating ring in the two‐coordinated bismuthinidene 9 exhibits significant aromatic character by delocalization of the bismuth lone pair.     

Lanthanide(II) Complexes of the Dihydrotriazinido Ligand [N{C(Ph)=N}2C(tBu)Ph]−

The potassium dihydrotriazinide K(L^Ph,tBu) ( 1 ) was obtained by a metal exchange route from [Li(L^Ph,tBu)(THF)₃] and KOtBu (L^Ph,tBu = [N{C(Ph)=N}₂C(tBu)Ph]). Reaction of 1 with 1 or 0.5 equivalents of SmI₂(thf)₂ yielded the monosubstituted Sm^II complex [Sm(L^Ph,tBu)I(THF)₄] ( 2 ) or the disubstituted [Sm(L^Ph,tBu)₂(THF)₂] ( 3 ), respectively. Attempted synthesis of a heteroleptic Sm^II amido‐alkyl complex by the reaction of 2 with KCH₂Ph produced compound 3 due to ligand redistribution. The Yb^II bis(dihydrotriazinide) [Yb(L^Ph,tBu)₂(THF)₂] ( 4 ) was isolated from the 1:1 reaction of YbI₂(THF)₂ and 1 . Molecular structures of the crystalline compounds 2 , 3· 2C₆H₆ and 4· PhMe were determined by X‐ray crystallography.     

Synthese und Eigenschaften der Di‐tert‐butylphosphide [M(PtBu2)2]2 (M = Zn,Hg) und [Cu(PtBu2)]4

Syntheses and Properties of Di‐tert‐butylphosphides [M(PtBu₂)₂]₂ (M = Zn, Hg) and [Cu(PtBu₂)]₄ The phosphides [M(PtBu₂)₂]₂ (M = Zn, Hg) and [Cu(PtBu₂)]₄ are accessible from reaction of LiPtBu₂ with ZnI₂, HgCl₂ and CuCl, respectively. [M(PtBu₂)₂]₂ (M = Zn, Hg) are dimers in the solid state. X‐ray structural analyses of these phosphides reveal that [M(PtBu₂)₂]₂ (M = Zn, Hg) contain four‐membered M₂P₂‐rings whereas [Cu(PtBu₂)]₄ features a planar eight‐membered Cu₄P₄‐ring. Degradation reaction of LiPtBu₂(BH₃) in the presence of HgCl₂ results in the dimeric phosphanylborane BH₃ adduct [tBu₂PBH₂(BH₃)]₂. X‐ray quality crystals of [tBu₂PBH₂(BH₃)]₂ (monoclinic, P2₁/n) are obtained from a pentane solution at 6 °C. According to the result of the X‐ray structural analysis, the O₂‐oxidation product of [Hg(PtBu₂)₂]₂, [Hg{OP(O)(tBu)OPtBu₂}(μ‐OPtBu)]₂, features in the solid state structure two five‐membered HgP₂O₂‐rings and a six‐membered Hg₂P₂O₂‐ring. Herein the spiro‐connected Hg atoms are member of one five‐membered and of the six‐membered ring.