Synthese und Strukturbestimmung von (tBuP)4Sn(CH3)2 und (CH3)2Sn[(tBu)P?P(tBu)]2Sn(CH3)2

Synthesis and Structure Analysis of (tBuP)₄Sn(CH₃)₂ and (CH₃)₂Sn[(tBu)P? P(tBu)]₂Sn(CH₃)₂ The diphosphides K₂[(tBu)P? (tBuP)₂? P(tBu)] 7 or K₂[(tBu)P? P(tBu)] 8 react with (CH₃)₂SnCl₂ in a molar ratio of 1 : 1 to form the binary 5-membered ring system P₄Sn 4 a and the 6-membered ring system Sn(P₂)₂Sn 5 a respectively. When (CH₃)₂SnCl₂, however, is treated with 8 in a molar ratio of 2 : 1 the 4-membered ring system P₃Sn 2 a is formed which includes the fragmentation of the intermediate K₂[(CH₃)₂Sn ((tBu)P? P(tBu))₂] 9. 4 a and 5 a could be obtained in a pure form and characterized NMR spectroscopically and by X-ray structure analyses; 2 a was identified only NMR spectroscopically.     

In situ-Erzeugung von [PX] und Insertion in (tBuP)3, (X = Cl,Br) Synthese der funktionalisierten Cyclophosphane (tBuP)3PX, [-(tBu)(X)P-2,3,4-(tBu)3]P4und Strukturbestimmung von (tBuP)3PCl

In situ Generation of [PX] and Insertion into (^tBuP)₃, (X = Cl, Br). Synthesis of the Functionalized Cyclophosphanes (^tBuP)₃PX, [1-(^tBu)(X)P-2,3,4-(^tBu)₃]P₄ and Structure Analysis of (^tBuP)₃PCl The redox system PX₃/SnX₂ (X = Cl, Br) can be used as a source for the in situ generation of halogenphosphanediyl [PX]. In the presence of tri-t-butylcyclotriphosphane (^tBuP)₃ the intermediately formed [PX] is added to a ring P atom followed by an insertion reaction, which leads to a ring expansion, whereby monohalogenocyclotetraphosphanes (^tBuP)₃PX (X = Cl, Br; 1, 2 ) are formed. Excess [PX] does not lead to further ring expansion but through a complex reaction course to the functionalized cyclotetraphosphanes [1-(^tBu)(X)P-2,3,4-(^tBu)₃]P₄, 3 (X = Br); 7 (X = Cl). 1, 2 and 3 could be obtained in a pure form and NMR and mass spectroscopically, 7 ³¹P-NMR spectroscopically, characterized. For 1 and 7 ³¹P? ^35,37Cl-isotopic shifts could be identified. 1 was further characterized by an X-ray structure analysis.     

Synthese der Silatetraphospholane (tBuP)4SiMe2, (tBuP)4SiCl2 und (tBuP)4Si(Cl)SiCl3 Molekül- und Kristallstruktur von (tBuP)4SiCl2

Synthesis of the Silatetraphospholanes (tBuP)₄SiMe₂, (tBuP)₄SiCl₂, and (tBuP)₄Si(Cl)SiCl₃ Molecular and Crystal Structure of (tBuP)₄SiCl₂ The reaction of the diphosphide K₂[(tBuP)₄] 7 with the halogenosilanes Me₂SiCl₂, SiCl₄ or Si₂Cl₆ in a molar ratio of 1:1 leads via a [4 + 1]-cyclocondensation reaction to the silatetraphospholanes (tBuP)₄SiMe₂ 1,1-dimethyl-1-sila-2,3,4,5-tetra-t-butyl-2,3,4,5-tetraphospholane, 1 , (tBuP)₄SiCl₂, 1,1-dichloro-1-sila-2,3,4,5-tetra-t-butyl-2,3,4,5-tetraphospholane, 2 , and (tBuP)₄Si(Cl)SiCl₃, 1-chloro-1-trichlorsilyl-1-sila-2,3,4,5-tetra-t-butyl-2,3,4,5-tetraphospholane, 3 , respectively, with the 5-membered P₄Si ring system. The reaction leading to 1 is accompanied with the formation of the by-product Me₂(Cl)-Si–(tBuP)₄–Si(Cl)Me₂ 1a (5:1), which has a chain structure. On warming to 100°C 1a decomposes to 1 and Me₂SiCl₂. The compounds 2 and 3 do not react further with an excess of 7 due to strong steric shielding of the ring Si atoms by the t-butyl groups. 1, 2 and 3 could be obtained in a pure form and characterized NMR spectroscopically; 2 was also characterized by a single crystal structure analysis. 1a was identified by NMR spectroscopy only.     

Synthese und Struktur von Hexa-t-butyl-1,4-dichloro-1,4-distanna-2,3,5,6,7,8-hexaphosphabicyclo[2.2.2]octan – Eine neue Käfigverbindung mit dem Sn(P2)3Sn-Gerüst

Synthesis and Structure of Hexa-t-butyl-1,4-dichloro-1,4-distanna-2,3,5,6,7,8-hexaphosphabicyclo[2.2.2]octane – a New Cage Compound with the Sn(P₂)₃Sn Skeleton The reaction of the diphosphide K₂[(tBuP)₂] 1 with SnCl₄ leads by a redox process mainly to (tBuP)_3,4 and other sideproducts. However, at the same time a threefold [2 + 1]-cyclocondensation reaction takes place yielding the new cage compound hexa-t-butyl-1,4-dichloro-1,4-distanna-2,3,5,6,7,8-hexaphosphabicyclo[2.2.2]octane, ClSn(tBuP? PtBu)₃SnCl 2 . 2 could be obtained in a pure form and characterized ³¹P and ¹¹⁹Sn NMR spectroscopically; 2 was also characterized by a single crystal structure analysis.     

Stannylierungsexperimente mit NH-funktionellen Aminoiminophosphoranen. Synthese und Struktur der tricyclischen Stannaphosphazene [Me2Sn(tBu2PN)NH]2 und [nBu2Sn(Ph2PN)2NH]2

Stannylation Experiments with NH-functional Aminoiminophosphoranes. Synthesis and Structure of the Tricyclic Stannaphosphazenes [Me₂Sn(^tBu₂PN)NH]₂ and [ⁿBu₂Sn(Ph₂PN)₂NH]₂ Aminoiminophosphoranes ^tBu₂P(NH)NH₂ ( 1 ) and (H₂NPPh₂)N(Ph₂PNH) ( 2 ) react with diaminostannanes R₂Sn(NEt₂)₂ by cyclocondensation to give cyclostannaphosphazenes [Me₂Sn(^tBu₂PN)NH]₂ ( 3 ) and [R₂Sn(Ph₂PN)₂NH]₂ ( 4 a , b ) ( a : R = Me, b : R = ⁿBu). With 2 and Me₃SnNEt₂ the ring compound Me₂Sn(Ph₂PN)₂NSnMe₃ ( 5 ) besides Me₄Sn is formed by per-N-stannylation and Sn-methyl group transfer. The crystal structures of 3 and 4 b were determined by X-ray structure analysis. 3 forms a planar heterotricyclus containing three four-membered rings with two pentacoordinated tin atoms (space group P 1 (No. 2); Z = 1). 4 b consists of a tricyclic molecule with two puckered six-membered rings and one planar four membered tin-nitrogen ring with two pentacoordinated tin atoms (space group P 1 (No. 2); Z = 1).     

(tBu2SnAsH)2 und (tBu2SnAsH)3: Zwei neue ring-oligomere Stannylarsine

(^tBu₂SnAsH)₂ and (^tBu₂SnAsH)₃: Two Novel Ring-Oligomeric Stannylarsines ^tBu₂SnCl₂ reacts with NaAsH₂ in liquid ammonia to give the four-membered As–H-functional stannylarsine (^tBu₂SnAsH)₂ ( 1 ). The oligomeric six-membered heterocycle (^tBu₂SnAsH)₃ ( 2 ) is obtained by transamination of ^tBu₂Sn(NH^tBu)₂ with AsH₃. The novel compounds are characterized by NMR (¹H, ¹¹⁹Sn) and mass spectroscopy and their molecule structures determined by X-ray crystallography. In the solid state both compounds contain molecules with planar tin-arsenic rings ( 1 : space group P2₁/n, Z = 2; 2 : space group P6₃/m, Z = 2).     

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.     

Reaktionen von (tBu)2P?PP(Br)tBu2 mit LiP(SiMe3)2, LiPMe2 und LiMe,LitBu, LinBu

Reactions of (tBu)₂P? P?P(Br)tBu₂ with LiP(SiMe₃)₂, LiPMe₂ and LiMe, LitBu and LinBu The reactions of (tBu)₂P? P?P(Br)tBu₂ 1 with LiP(SiMe₃)₂ 2 yield (Me₃Si)₂P? P(SiMe₃)₂ 4 and P[P(tBu)₂]₂P(SiMe₃)₂ 5 , whereas 1 with LiPMe₂ 2 yields P₂Me₄ 6 and P[(tBu)₂]₂PMe₂ 7 . 1 with LiMe yields the ylid tBu₂P? P?P(Me)tBu₂ (main product) and [tBu₂P]₂PMe 15 . In the reaction of 1 with tBuLi [tBu₂P]₂PH 11 is the main product and also tBuP? P?P(R)tBu₂ 21 is formed. The reaction of 1 with nBuLi leads to [tBu₂P]₂PnBu 17 (main product) and tBu₂P? P?P(nBu)tBu₂ 22 (secondary product).     

Reaktionen des tBu(Me3Si)P?P(Li)?P(tBu)2 mit CH3Cl und 1,2-Dibromethan

Reactions of tBu(Me₃Si)P? P(Li)? P(tBu)₂ with CH₃Cl and 1,2-Dibromoethane tBu(Me₃Si)P? P(Li)? P(tBu)₂ · 0.95 THF 1 with CH₃Cl (?70°C) yields tBu(Me₃Si)P? P = P(Me)(tBu)₂ 2 at ?70°C, with 1,2-Dibromoethane tBu(Me₃Si)P? PBr? P(tBu)₂ 3 (main product) and tBu(Me₃Si)P? P?P(Br)tBu₂ 4. 3 eliminates Me₃SiBr yielding the cyclotetraphosphane {tBuP? P[P(tBu)₂]}₂ 5 .     

Cyclische Diazastannylene. XXVIII. Anorganische Polycyclen aus der Reaktion eines Bis(amino)-stannylens bzw. eines Iminostannylens mit SnCl2, SnBr2 und tert-Butoxizinn(II)-chlorid bzw. -bromid

Cyclic Diazastannylenes. XXVIII. Inorganic Polycyclic Compounds from the Reaction of Bis(amino)stannylene or Iminostannylene with SnCl₂, SnBr₂, and tert-Butoxitin(II) Chloride or Bromide The cyclic bis(amino)stannylene 1 may react with tert-butoxitin(II) chloride or bromide yielding a Lewis acid-base adduct 4 resp. 5 , in which the two molecules are held together via N→Sn (233.8(3) pm) and O→Sn (215.1(2) pm) bonds. The resulting adduct 4 contains therefore two four membered rings sharing one common edge as found by X-ray structure determination. If 1 is allowed to react with SnCl₂ or SnBr₂, the salts Me₂Si(N^tBu)₂Sn₂Br⁺Sn₂Br₅^? ( 7 ) are formed. Structure analysis reveals the cations in 6 and 7 to be very similar: SnCl⁺ and SnBr⁺ are coordinated by the “trihapto ligand” 1 in a way resulting a polycyclic SiN₂Sn₂X-arrangement. To a central Sn₂N₂ tetrahedron Si and halogen X are added occupying and bridging two opposite edges (mean values: N? Sn = 232(5) ( 6 ), N? Sn = 230(2) ( 7 ), Sn? C1 = 265(1), Sn? Br = 275(1) pm). The reaction intermediate (SnN^tBu)₂ adds to SnCl₂ to form the crystalline polymer ( ^tBuN)₂Sn₃C1₂ (8) . X-ray structure determination reveals the solid to be built up by one-dimensional chains of polycyclic Sn₃(N^tBu)₂C1₃ sharing two chlorine atoms with neighbouring units. The unit Sn₃(N^tBu)₂C1₃ can be visualized as an equilateral triangle of chlorine atoms, on which a smaller triangle of tin atoms is superimposed; the corners of the smaller triangle being located in the middle of the larger triangle's edges. The tin atoms are bipyramidally coordinated by two N? ^tBu-groups thus forming a nearly perfect Sn₃N_2s trigonal bipyramide (Sn? N = 222.7(3) pm). Two chlorine atoms of the triangle are connected to neighbouring units, the chlorine atoms thus attain an unusual nearly square-planar coordination sphere (Sn? Cl(mean) = 308(5) pm). The tertbutyl groups at the nitrogen atoms “screen” the inorganic part of the structure leading to a layer structure.     

Zur Reaktivität des Ferriophosphaalkens (Z)‐[Cp*(CO)2FeP=C(tBu)NMe2] gegenüber Propiolsäureestern HC≡C‐CO2R (R=Me,Et) und Acetylendicarbonsäureestern RO2C‐C≡C‐CO2R (R=Me,Et, tBu)

On the Reactivity of the Ferriophosphaalkene (Z)‐[Cp*(CO)₂Fe‐P=C(tBu)NMe₂] towards Propiolates HC≡C‐CO₂R (R=Me, Et) and Acetylene Dicarboxylates RO ₂C‐C≡C‐CO₂R (R=Me, Et, tBu) The reaction of equimolar amounts of (Z)‐[Cp*(CO)₂Fe‐P=C(tBu)NMe₂] 3 and methyl‐ and ethyl‐propiolate ( 2a, b ) or of 3 and dialkyl acetylene dicarboxylates 1a (R=Me), 1b (Et), 1c (tBu) afforded the five‐membered metallaheterocycles [Cp*(CO) =C(tBu)NMe₂] ( 4a, b ) and [Cp*(CO) =C(tBu)NMe₂] ( 5a—c ). The molecular structures of 4b and 5a were elucidated by single crystal X‐ray analyses. Moreover, the reactivity of 4b towards ethereal HBF₄ was investigated.     

Neue phosphidoverbrückte Mehrkernkomplexe des Ag und Zn. Die Kristallstrukturen von [Ag3(PPh2)3(PnBu2tBu)3], [Ag4(PPh2)4(PR3)4] (PR3 = PMenPr2, PnPr3), [Ag4(PPh2)4(PEt3)4]n, [Zn4(PPh2)4Cl4(PRR2)2] (PRR′2 = PMenPr2, PnBu3, PEt2Ph), [Zn4(PhPSiMe3)4Cl4(C4H8O)2] und [Zn4(PtBu2)4Cl4]

New Phosphido-bridged Multinuclear Complexes of Ag and Zn. The Crystal Structures of [Ag₃(PPh₂)₃(PⁿBu₂^tBu)₃], [Ag₄(PPh₂)₄(PR₃)₄] (PR₃ = PMeⁿPr₂, PⁿPr₃), [Ag₄(PPh₂)₄(PEt₃)₄]_n, [Zn₄(PPh₂)₄Cl₄(PRR′₂)₂] (PRR′₂ = PMeⁿPr₂, PⁿBu₃, PEt₂Ph), [Zn₄(PhPSiMe₃)₄Cl₄(C₄H₈O)₂] and [Zn₄(P^tBu₂)₄Cl₄] AgCl reacts with Ph₂PSiMe₃ in the presence of tertiary Phosphines (PⁿBu₂^tBu, PMeⁿPr₂, PⁿPr₃ and PEt₃) to form the multinuclear complexes [Ag₃(PPh₂)₃(PⁿBu₂^tBu)₃] 1 , [Ag₄(PPh₂)₄(PR₃)₄] (PR₃ = PMeⁿPr₂ 2 , PⁿPr₃ 3 ) and [Ag₄(PPh₂)₄(PEt₃)₄]_n 4 . In analogy to that ZnCl₂ reacts with Ph₂PSiMe₃ and PRR′₂ to form the multinuclear complexes [Zn₄(PPh₂)₄Cl₄(PRR′₂)₂] (PRR′₂ = PMeⁿPr₂ 5 , PⁿBu₃ 6 , PEt₂Ph 7 ). Further it was possible to obtain the compounds [Zn₄(PhPSiMe₃)₄Cl₄(C₄H₈O)₂] 8 and [Zn₄(P^tBu₂)₄Cl₄] 9 by reaction of ZnCl₂ with PhP(SiMe₃)₂ and ^tBu₂PSiMe₃, respectively. The structures were characterized by X-ray single crystal structure analysis. Crystallographic data see “Inhaltsübersicht”.     

Beiträge zur Chemie des Phosphors. 128. Synthese des Diphosphastanna-cyclopropans (t-BuP)2Sn(t-Bu)2

Contributions to the Chemistry of Phosphorus. 128. Synthesis of the Diphosphastanna-cyclopropane (t-BuP)₂Sn(t-Bu)₂ The first three-membered P₂Sn heterocycle, 1,2,3,3-tetra-tert-butyl-1,2,3-diphosphastanna-cyclopropane (1,2,3,3-tetra-tert-butyl-1,2,3-diphosphastannirane) ( 1 ), has been synthesized by [2+1] cyclocondensation of K(t-Bu)P—P(t-Bu)K with (t-Bu)₂SnCl₂. 1 is stable at room temperature. Besides, (t-BuP)₂[Sn(t-Bu)₂]₂ ( 2 ), (t-BuP)₄Sn(t-Bu)₂ ( 3 ), and (t-BuP)₄ are formed. In the reaction with Et₂SnCl₂, the six-membered ring compound [(t-BuP)₂SnEt₂]₂ ( 4 ) is the main-product; the four- and five-membered cyclostannaphosphanes (t-BuP)₃SnEt₂ ( 5 ) and (t-BuP)₃(SnEt₂)₂ ( 6 ) are also formed. 1 could be isolated in the pure state and has been unambiguously characterized as a three-membered heterocycle with a P₂Sn skeleton. The ³¹P-NMR parameters of the other new cyclostannaphosphanes 2–6 are reported.     

Die Bildung von [(tBu)2P]2P?P[P(tBu)2]2 aus LiP[P(tBu)2]2 und 1,2-Dibromethan. Die Thermolyse von tBu2P?PP(Br)tBu2

[(tBu)₂P]₂P? P[P(tBu)₂]₂ from LiP[P(tBu)₂]₂ and 1,2-Dibromomethane. Pyrolysis of tBu₂P? P?P(Br)tBu₂ All products of the reaction of [tBu₂P]₂PLi 1 with 1,2-dibromoethane 2 were investigated. Already at ?70°C tBu₂P? P?P(Br)tBu₂ 3 as main product and [tBu₂P]₂PBr 4 are formed. Only with an excess of 1 also [tBu₂P]P? P[P(tBu)₂]₂ 5 is obtained. Warming of a pure solution of 3 in toluene from ?70°C to ?30°C leads to 4 , and at 20°C tBu₂PBr and the cyclophosphanes P₄[P(tBu)₂]₄ and P₃[P(tBu)₂]₃ are observed. 5 does not result from 3 , it's rather a byproduct from the reaction of 1 with 4 . Also the ylide 3 and 1 yields 5 .     

Strukturelle Vielfalt im pseudo‐ternären System M/Ge/I: α‐[NMe(nBu)3](GeI4)I, β‐[NMe(nBu)3](GeI4)I und [ImMe(nBu)][N(nBu)4](GeI4)3I2

By reaction of GeI₄, [N(nBu)₄]I as iodide donor, and [NMe(nBu)₃][N(Tf)₂] as ionic liquid, reddish‐black, plate‐like shaped crystals are obtained. X‐ray diffraction analysis of single crystals resulted in the compositions ;alpha;‐[NMe(nBu)₃](GeI₄)I (Pbca; a = 1495.4(3) pm; b = 1940.6(4) pm; c = 3643.2(7) pm; Z = 16) and β‐[NMe(nBu)₃](GeI₄)I (Pn; a = 1141.5(2) pm; b = 953.6(2) pm; c = 1208.9(2) pm; β = 100.8(1)°; Z = 2). Depending on the reaction temperature, the one or other compound is formed selectively. In addition, the reaction of GeI₄ and [N(nBu)₄]I, using [ImMe(nBu)][BF₄] (Im = imidazole) as ionic liquid, resulted in the crystallization of [ImMe(nBu)][N(nBu)₄](GeI₄)₃I₂ (P2₁/c; a = 1641.2(3) pm; b = 1903.0(4) pm; c = 1867.7(4) pm; β = 92.0(1)°; Z = 4). The anionic network of all three compounds is established by molecular germanium(IV)iodide, which is bridged by iodide anions. The different connectivity of (GeI₄–I^–) networks is attributed to the flexibility of I^– regarding its coordination and bond length. Here, a [3+1]‐, 4‐ and 5‐fold coordination is first observed in the pseudo‐ternary system M/Ge/I (M: cation).     

Synthese und Eigenschaften von Triphenylzinnmolybdaten mit kettenförmigen Anionen des Typs 1∞[(Ph3Sn)MoO4]–. Die Kristallstrukturen von (nPr4N)[(Ph3Sn)MoO4]·CH3CN, (nBu4N)[(Ph3Sn)MoO4], [Zn(en)2(Ph3Sn)2(MoO4)2]·2DMF·EtOH und [Cu(en)2(Ph3Sn)2(MoO4)2]·2DMF·EtOH

The reaction of Ph₃SnCl, (R₄N)₂[Mo₆O₁₉] and (R₄N)OH in a molar ratio of 6:1:10 leads to the formation of (R₄N)[(Ph₃Sn)MoO₄] (R = ⁿPr ( 1 ), ⁿBu ( 2 )). Compounds 1· CH₃CN and 2 have been charactarized by IR spectroscopy and single crystal X‐ray diffraction. 1· CH₃CN forms orthorhombic crystals, space group P2₁2₁2₁ with a = 1339.9(2), b = 1508.9(2), c = 1733.2(3) pm. 2 crystallizes in the monoclinic space group P2₁ with a = 1342.6(2), b = 2280.3(4), c = 1344.0(2) pm, β = 118.34(1). Both compounds 1 and 2 consist of isolated R₄N⁺ cations and polymeric $\rm^{1}_{\infty}$ [(Ph₃Sn)MoO₄]^– chains with an alternating arrangement of Ph₃Sn⁺ and MoO₄^2– groups. Treatment of (Ph₃Sn)₂MoO₄ with bis(ethylenediamine)copper(II) succinate yields [Cu(en)₂(Ph₃Sn)₂(MoO₄)₂] ( 3 ). The zinc derivative [Zn(en)₂(Ph₃Sn)₂(MoO₄)₂] ( 4 ) is obtained similarly by reaction of (Ph₃Sn)₂MoO₄ with bis(ethylenediamine)zinc(II) formiate. Compounds 3· 2DMF · EtOH and 4· 2DMF · EtOH crystallize in the monoclinic space group P2₁/n with a = 1998.0(2), b = 1313.3(1), c = 2181.6(2) pm, β = 90.97(1)° for 3 and a = 2015.4(1), b = 1316.7(1), c = 2157.0(1) pm, β = 90.40(1)° for 4 . Like in the cases of 1 and 2, polymeric $\rm^{1}_{\infty}$ [(Ph₃Sn)MoO₄]^– chains are observed. The [M(en)₂]²⁺ units (M = Cu, Zn) act as linkers between the $\rm^{1}_{\infty}$ [(Ph₃Sn)MoO₄]^– chains to give 2D layer structures with (6, 3) net topology.     

丙酮酸异烟酰腙四核有机锡配合物的合成、表征及{[nBu2Sn(C9H8N3O3)O]SnBu3n}2的晶体结构

The tetranuclear alkyltin(Ⅳ) compounds {[R2Sn(C9H8N3O3)O]SnR3}2 [R=n-Bu (1), 4-CNC6H4CH2 (2),C6H5CH2 (3), 4-ClC6H4CH2 (4)] were prepared by the reaction of Schiff base ligand pyruvic acid isonicotinyl hydrazone with (R3Sn)2O in the corresponding molar ratio of 1:1. All compounds have been characterized by elemental analysis, IR and ^1H NMR spectra. The crystal structure of compound 1 was determined by X-ray single crystal diffractional analysis. This compound exhibits a dimeric structure containing distannoxane units with two types of the tin atoms. For the first tin atom, it appears to be seven-coordinated with a distorted pentagonal bipyramid geometry, and the other is five-coordinated with a distorted trigonal bipyramidal geometry. The molecules are packed in the unit cell in two-dimensional network structure through an interaction between the N atoms of the pyridine and the tin atoms of an adjacent molecule.     

1,1‐Diethyl‐1‐germa‐2,3,4,5‐tetra‐tert‐butyl‐2,3,4,5‐tetraphospholan (C2H5)2Ge(tBuP)4, Molekül‐ und Kristallstruktur

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.     

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.     

Phosphinophosphiniden-Phosphorane tBu2P?P = P(R)tBu2 aus Li(THF)2[η2-(tBu2P)2P] und Alkylhalogeniden

The Phosphinophosphinidene-phosphoranes ^tBu₂P? P = P(R)^tBu₂ from Li(THF)₂[η²-(^tBu₂P)₂P] and Alkyl Halides We report the formation of ^tBu₂P? P = P(R)^tBu₂ a and (^tBu₂)₂PR b (with R = Me, Et, ⁿPr, ⁱPr, ⁿBu, PhCH₂, H₂C = CH? CH₂ and CF₃) reactions of Li(THF)₂[η²-(^tBu₂P)₂P] 2 with MeCl, MeI, EtCl, EtBr, ⁿPrCl, ⁿPrBr, ⁱPrCl, ⁿBuBr, PhCH₂Cl, H₂C = CH? CH₂Cl or CF₃Br. In THF solutions the ylidic compounds a predominate, whereas in pentane the corresponding triphosphanes b are preferrably formed. With ClCH₂? CH = CH₂ only b is produced; CF₃Br however yields both ^tBu₂P? P = P(Br)^tBu₂ and ^tBu₂P? P = P(CF₃)^tBu₂, but no b . The ratio of a:b is influenced by the reaction temperature, too. The compounds ^tBu₂P? P = P(Et)^tBu₂ 4a and (^tBu₂P)₂PEt 4 b , e. g., are produced in a ratio of 4:3 at ?70°C in THF, and 1:1 at 20°C; whereas 1:1 is obtained at ?70°C in pentane, and 1:2 at 20°C. Neither ^tBuCl nor H₂C = CHCl react with 2 . The compounds a decompose thermally or under UV irradiation forming ^tBu₂PR and the cyclophosphanes (^tBu₂P)_nP_n.