Alkoholyse von Tris(dimethylamino)-arsin

Alcoholysis of Tris (dimethylamino)arsine The reaction of tris(dimethylamino)arsine with alcoholes and thioles leads to the formation of esters of the general formula As(XR)₃ (X = O and S). The reaction is a suitable preparative method for the synthesis of the esters As(XR)₃ (X = O and S). By alcoholysis in steps results an equilibrium system containing the molecules AsX₃, AsX₂Y, AsXY₂, and AsY₃ (X = OR, Y = N(CH₃)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.     

Zinn(II)-halogenid-Komplexe mit Tri-tert-butylphosphin und Tris(dimethylamino)phosphin

Tin(II) Halide Complexes with Tri-tert-butylphosphine and Tris(dimethylamino)-phosphine TIn(II) chloride and tin(II) bromide react with tri-tert-butylphosphine and with tris(dimethylamino)phosphine to give stable 1:1 adducts. Infrared and raman data as well as¹H-n.m.r., ³¹P-n.m.r., and ^119mSn-Mössbauer spectra of the novel phosphine dihalogennostannylenes are discussed in terms of an ylidic type of bonding.     

Synthese der Stannatetraphospholane (tBuP)4SnR2 (R = tBu,nBu, C6H5) und (tBuP)4Sn(Cl)nBu Molekül- und Kristallstruktur von (tBuP)4Sn(tBu)2

Synthesis of the Stannatetraphospholanes (tBuP)₄SnR₂ (R = tBu, nBu, C₆H₅) and (tBuP)₄Sn(Cl)nBu Molecular and Crystal Structure of (tBuP)₄Sn(tBu)₂ The reaction of the diphosphide K₂[tBuP-(tBuP)₂-PtBu] 4 with the halogenostannanes (tBu)₂SnCl₂, (nBu)₂SnCl₂, (C₆H₅)₂SnCl₂ or nBuSnCl₃ in a molar ratio of 1 : 1 leads via a [4 + 1]-cyclocondensation reaction to the stannatetraphospholanes (tBuP)₄SnR₂ 3 b–3 d and (tBuP)₄Sn(Cl)nBu 3 e , respectively, with the binary 5-membered P₄Sn ring system. 3 b was characterized by a single crystal structure analysis; the 5-membered ring exists in a planar conformation. The compounds 3 b–3 e were identified by NMR and also by mass spectroscopy; the ³¹P{¹H}-NMR spectra of 3 b–3 d showed an AA′MM′ (AA′MM′X), 3 e on the other hand an ABCD (ABCDX) spin system.     

1,2-Bis(dimethylamino)-3,4,5-triphenyl-3,4,5-triphospha-1,2-diborolan und 1,2-Bis(dimethylamino)-3,4,5,6-tetra-tbutyl-3,4,5,6-tetraphospha-1,2-diborin: Synthese und Struktur sowie Berechnungen zur Molekülstruktur

1,2-Bis(dimethylamino)-3,4,5-triphenyl-3,4,5-triphospha-1,2-diborolane and 1,2-Bis(dimethylamino)-3,4,5,6-tetra-tbutyl-3,4,5,6-tetraphospha-1,2-diborine: Synthesis and Structure as well as Calculations on the Molecular Structure The diphosphides K₂[(C₆H₅)P? (C₆H₅)P? P(C₆H₅)], 4 or K₂[(tBuP)? (tBuP)₂? P(tBu)], 5 , react with (ClBNMe₂)₂ to form the binary 5-membered ring system 1,2-bis(dimethylamino)-3,4,5-triphenyl-3,4,5-triphospha-1,2-diborolane (C₆H₅P)₃(BNMe₂)₂, 2a , and the 6-membered ring system 1,2-bis(dimethylamino)-3,4,5,6-tetra-tbutyl-3,4,5,6-tetraphospha-1,2-diborine, (tBuP)₄(BNMe₂)₂, 3a , respectively. 2a and 3a could be obtained in a pure form and characterized NMR spectroscopically and by X-ray structure analyses. The two ring systems are folded; 2a exists in the ?envelope”?- 3a in the ?boat”?-conformation. Ab initio computations for 3,4,5-triphospha-1,2-diborolane M5 show that the global minimum is characterized by one B? P double bond. The parent compound geometry M6 is characterized by transannular bonding in the PH? BH? BH? PH moiety which differs in character from those in the four- and five-membered rings (BH)₂(PH)₂ and (BH)₂(PH)₃ M5 d , respectively. Explicit calculation of the influence of amino substituents on boron improved agreement of the bond length between computed and X-ray data.     

Die Reaktionen von tBu2P–P=P(Me)tBu2 und (Me3Si)tBuP–P=P(Me)tBu2 mit PR3

The Reactions of ^tBu₂P–P=P(Me)^tBu₂ and (Me₃Si)^tBuP–P=P(Me)^tBu₂ with PR₃ ^tBu₂P–P=P(Me)^tBu₂ ( 1 ) reacts at 20 °C with PMe₃, PEt₃, P(c‐Hex)₃, P(p‐Tol)₃, PPh₂Me, PPh₂Et, PPhEt₂, PPh₂ⁱPr, PPh₃ and P(NEt₂)₃ yielding ^tBu₂P–P=PR₃ and ^tBu₂PMe; however, P^tBu₃, P^tBu₂(SiMe₃) and ^tBu₂PCl don't. ^tBu₂PH and 1 form ^tBu₂P–PH–P^tBu₂ which yields ^tBu₂P–P=PEt₃ when treated with PEt₃. Ph₂PH, ^tBuPH₂, PH₃, Ph₂PCl and EtOH don't substitute the ^tBu₂PMe group in 1 , instead, the molecule is decomposed. With PEt₃, (Me₃Si)^tBuP–P=P(Me)^tBu₂ forms (Me₃Si)^tBuP–P=PEt₃. The compounds ^tBu₂P–P=PR₃ decompose at 20 °C to different degrees giving P‐rich consecutive products of the phosphinophosphinidene.     

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.     

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.     

Über Tris[(trialkylphosphan)gold(I)]oxonium-tetrafluoroborate und Tris[(triphenylphosphan)gold(I)]sulfonium-tetrafluoroborat

On Tris[(trialkylphosphine)gold(I)]oxonium Tetrafluoroborates and Tris[(triphenylphosphine)gold(I)]sulfonium Tetrafluoroborate [Et₃PAu]⁺BF, obtained from Et₃PAuCl and AgBF₄ in tetrahydrofuran, reacts with KOH (molar ratio 3:1) to give the oxonium salt [(Et₃P)Au]₃O⁺BF ( 1 ). The homologous [^t(Bu₃P)Au]₃O⁺BF ( 2 ) is generated similarly from ^tBu₃PAuCl and Ag₂O in the presence of NaBF₄ in THF. The composition and identity of these two first tris[(tri alkyl phosphine)gold(I)]oxonium salts have been confirmed by analytical and spectroscopic data. The compounds are useful aurating agents. From the corresponding triphenylphosphine complex and (Me₃Si)₂S quantitative yields of the sulfonium salt [(Ph₃P)Au]₃S⁺BF ( 3 ) are obtained. Its crystal structure features monomeric cations, and in these small Au? S? Au angles indicate significant metal-metal bonding.     

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.     

Derivate des Phosphorsäure-o-phenylenesters. 32. Reaktion von Tris(dimethylamino)phosphin mit Pv-Halogeniden

Derivatives of o-Phenylene Phosphate. 32. Reaction of Tris(dimethylamino)phosphine with Phosphorus(V) Halides The reactions of the Tris(dimethylamino)phosphine with P^v Halides give both the products of the substitution reaction and the products of the redox reaction.     

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.     

Das unterschiedliche Reaktionsverhalten von basefreiem Tris(trimethylsilyl)methyl‐Lithium gegenüber den Trihalogeniden der Erdmetalle und des Eisens

The Variable Reaction Behaviour of Base‐free Tris(trimethylsilyl)methyl Lithium with Trihalogenides of Earth‐Metals and Iron Base‐free tris(trimethylsilyl)methyl Lithium, Tsi–Li, reacts with the earth‐metal trihalogenides (MHal₃ with M = Al, Ga, In and Hal = Cl, Br, I) primarily to give the metallates [Tsi–MHal₃]Li. Simultaneous to this simple metathesis a methylation also takes place, mainly with heavier halogenides of Ga and In with excess Tsi–Li, forming the mono and dimethyl compounds Tsi–M(Me)Hal (M = Ga, In; Hal = I), Tsi–MMe₂ (M = Ga), and the bis(trisyl)derivative (Tsi)₂InMe, respectively and the main by‐product 1,3‐disilacyclobutane. Representatives of each type of compound have been isolated by fractionating crystallizations or sublimations and characterized by spectroscopic methods (¹H, ¹³C, ²⁹Si NMR, IR, Raman) and X‐ray elucidations. Reduction takes place, when FeCl₃ reacts with Tsi–Li (1 : 3 ratio) in toluene at 55–60 °C, yielding red‐violet Fe(Tsi)₂, 1,1,1‐tris(trimethylsilyl)‐2‐phenyl ethane and low amounts of Tsi–Cl. Fe(Tsi)₂ is monomeric, crystallizes in the monoclinic space group C2/c and consists of a linear C–Fe–C skeleton with d(Fe–C) of 204,5(4) pm.     

Bisaminophosphane – Synthese,Struktur und Reaktivität

Bisaminophosphanes – Synthesis, Structure, and Reactivity Different pathways for the synthesis of bis(alkylamino)phosphanes RP(N(H)R′)₂ are described. t‐BuP(N(H)‐ Dipp)₂ (Dipp = 2,6‐i‐Pr₂–C₆H₃) was structurally characterized by single crystal X‐ray diffraction. The reactivity of the compounds was examplarily investigated using t‐BuP(N(H)t‐Bu)₂. Its reaction with Me₃Al and R₂AlH (R = Me, Et, i‐Bu) in 1 : 1 and 1 : 2 stoichiometrie yield monosubstituted compounds of the type t‐BuP(N(H)t‐Bu)(N(AlR₂)t‐Bu).     

Tris[3‐hydroxy‐2(1 H)‐pyridinonato]‐Komplexe von Al3+, Cr3+ und Fe3+ – Kristall‐ und Molekülstrukturen von 3‐Hydroxy‐2(1 H)‐pyridinon und Tris[3‐hydroxy‐2(1 H)‐pyridinonato]chrom(III)

Tris[3‐hydroxy‐2(1 H)‐pyridinonato] Complexes of Al³⁺, Cr³⁺, and Fe³⁺ – Crystal and Molecular Structures of 3‐Hydroxy‐2(1 H)‐pyridinone and Tris[3‐hydroxy‐2(1 H)‐pyridinonato]chromium(III) Tris[3‐hydroxy‐2(1 H)‐pyridinonato] complexes of Al³⁺, Cr³⁺ and Fe³⁺ are obtained by reactions of 3‐hydroxy‐2(1 H)pyridinone with the hydrates of AlCl₃, CrCl₃ or Fe(NO₃) in aqueous alkaline solutions as polycrystalline precipitates. The compounds are isotypic. X‐ray structure determinations were performed on single crystals of the uncoordinated 3‐hydroxy‐2(1 H)‐pyridinone ( 1 ) (orthorhombic, space group P2₁2₁2₁, a = 405.4(1), b = 683.0(1), c = 1770.3(3) pm, Z = 4) and of the chromium compound 3 (rhombohedral with hexagonal setting, space group R3c, a = 978.1(1), c = 2954.0(1) pm, Z = 6).     

(O,O′)-Diorganodithiophosphatophenyltellur(II)- und Tris[(O,O′)-diorganodithiophosphato]phenyltellur(IV)-Verbindungen; Kristallstruktur von Tris[(O,O′)-diphenyldithiophosphato]phenyltellur(IV)

(O,O′)-Diorganodithiophosphatophenyltellurium(II)- and Tris[(O,O′)-diorganodithiophosphato]phenyltellurium(IV) Compounds; Crystal Structure of Tris[(O,O′)-diphenyldithiophosphato]phenyltellur(IV) The title compounds are available by reaction of trichlorophenyltellurium(IV) respectively iodophenyltellurium(II) with the sodium or ammonium salts of (O,O′)-diorganodithiophosphorus acids in various solvents. The resulting tellurium(IV) compounds have a pronounced tendency towards reductive elimination of bis[(O,O′)-diorganothiophosphoryl]disulfanes [S₂P(OR)₂]₂ in solution. In contrast, the tellurium(II) compounds are stable, although they are disintegrated to diphenylditellane and [S₂P(OR)₂]₂ on prolonged standing in chlorinated hydrocarbons. Crystals of tris[(O,O′)-diphenyldithiophosphato]phenyltellurium(IV) are monoclinic (space group P2₁/c) with the cell constants: a = 1 039.2(1), b = 1 037.9(3), c = 4 205.0(1) pm, β = 95.273(1)°, V = 4 516.42(9)X10⁶ pm³, Z = 4. The compound appears to be monomeric in the solid state forming a distorted pentagonal bipyramid. The stereochemical influence of the lone pair of electrons causes the axial (i. e. C1? Te? S4) angle to be 156.6(1)° rather than the theoretical 180°.     

Synthese,Charakterisierung und Struktur von P7(t-Bu3Si)3 („Tris(supersilyl)heptaphosphan(3)”︁)

Synthesis, Characterization, and Structure of P₇(t-Bu₃Si)₃ (?Tris(supersilyl)heptaphosphane(3)”? Tris(tri-tert-butylsilyl)heptaphosphanortricyclane P₇(t-Bu₃Si)₃ 1 is obtained from the reaction of (t-Bu)₃Si? Si(t-Bu)₃ with white phosphorus and forms colorless to pale yellow thermostable crystals. 1 is identified by the complete analysis of its ³¹P{¹H} NMR spectrum (A[MX]₃ spin system) as well as by a single crystal structure determination (space group Pca2₁, a = 170.76(2)pm, b = 131.14(3)pm, c = 426.61(5)pm, α = β = γ= 90°, Z = 8 formula units in the elementary cell). The steric demand of the (t-Bu)₃Si-Groups causes an increase of the exocyclic bond angles at the equatorial phosphorus atoms P^e, while it does not particularly influence the P₇-skeleton. Chlorine (r.t.) and bromine (70°C) degrade the P₇-cage of 1 with formation of PX₃ and (t-Bu)₃SiX (X = Cl, Br).     

Über die Synthese von Tris(trimethylsilyl)silyl-kalium, -rubidium und -caesium und die Molekülstrukturen zweier Toluolsolvate

About the Synthesis of Tris(trimethylsilyl)silyl Potassium, Rubidium and Cesium and the Molecular Structures of two Toluene Solvates . Solventfree tris(trimethylsilyl)silyl potassium ( 1 ), rubidium ( 2 ) and cesium ( 3 ) are obtained by the reaction of the zink group bis[tris(trimethylsilyl)silyl] derivatives with the appropriate alkali metal in n-pentane. Addition of benzene or toluene to the colourless powders yields deeply coloured solutions. From these solutions single crystals of tris(trimethylsilyl)silyl rubidium—toluene (2/1) ( 2 a ) and tris(trimethylsilyl)silyl cesium—toluene (2/3) ( 3 a ) suitable for X-ray structure analysis are iso- lated [ 2a : orthorhombic; P2₁2₁2₁; a = 1 382.1(3); b = 1 491.7(5); c = 2 106.3(6) pm; Z = 4 (dimers); 3a : orthorhombic; P2₁2₁2₁; a = 2 131.0(6); b = 2 833.1(2); c = 925.2(2) pm; Z = 4 (dimers)]. The central structure moieties are folded four-membered Rb₂Si₂ and Cs₂Si₂ rings, respectively. Small Si? Si? Si angles (100 to 104°) on the one hand and extreme highfield ²⁹Si-NMR shifts of the central silicon atoms on the other hand indicate a strong charge transfer from the alkali metal atoms to the tris(trimethylsilyl)silyl fragments, i.e. mainly ionic interactions between alkalimetal and silicon atoms.     

Tris(trimethylsilyl)methanselenenylhalogenide und -chalkogenide

Tris(trimethylsilyl)methaneselenenyl Halides and Chalcogenides . Ditrisyldiselenide ( 1 ) (trisyl = TSi = (Me₃Si)₃C) reacts with SOCl₂, Br₂ and I₂ to provide trisylselenenyl halides TSiSeX ( 2 : X = Cl; 3 : X = Br, 4 : X = I). Insertion of S and Se into the Se? Se bond of 1 to yield (TSiSe)₂S_n ( 5 : n = 1; 6 : n = 2) and (TSiSe)₂Se_n ( 7 : n = 1; 8 : n = 2) was catalysed by iodine. 5 was isolated in pure state and examined by X-ray diffraction. Triselenide 7 can be cleaved by I₂ in CS₂ to give 4 and Se₂I₂ ( 9 ). From 2 with Me₃SiCN and Me₃SiNCS, the new selenenyl pseudohalides TSiSeCN ( 10 ) and TSiSeSCN ( 11 ) were prepared. The compounds were characterised by ¹H, ¹³C- and ⁷⁷Se n.m.r. spectra.     

Reaktionen von Zink- und Cadmiumhalogeniden mit Tris(trimethylsilyl)phosphan und Tris(trimethylsilyl)arsan

Reactions of Zinc and Cadmium Halides with Tris(trimethylsilyl)phosphane and Tris(trimethylsilyl)arsane ZnCl₂ reacts with E(SiMe₃)₃ (E = P, As) in toluene in the presence of PⁿPr₃ to give the binuclear complexes [Zn₂Cl₂{E(SiMe₃)₂}₂(PⁿPr₃)₂] · C₇H₈ (E = P 1 , As 2 ). Therefore by the use of PⁱPr₃ clusters consisting of ten metal atoms are obtained, [Zn₁₀Cl₁₂(ESiMe₃)₄(PⁱPr₃)₄] (E = P 3 , As 4 ). As a result of the reaction of CdBr₂ with P(SiMe₃)₃ the compound [CdBr₂{P(SiMe₃)₃}]₂ ( 5 ) can be isolated at –40 °C. In the presence of PⁿPr₃ CdBr₂ reacts with P(SiMe₃)₃ forming the binuclear complex [Cd₂Br₂{P(SiMe₃)₂}₂(PⁿPr₃)₂] · thf ( 6 ). The same reaction with PⁱPr₃ yields to the cluster [Cd₁₀Br₁₂(PSiMe₃)₄{P(SiMe₃)₃}₄] · 2 C₇H₈ ( 7 ). ZnI₂ and CdI₂ react with As(SiMe₃)₃ to yield the complexes [MI₂{As(SiMe₃)₃}]₂ (M = Zn 8 , Cd 9 ). In the case of CdI₂ additionally the cluster [Cd₁₀I₁₂(AsSiMe₃)₄ · {As(SiMe₃)₃}₄] · 4,5 C₇H₈ ( 10 ) is formed which is analogous to the compounds 3 , 4 and 7 . In the presence of [PⁿBu₄]I 8  reacts in THF to give the ionic compound [PⁿBu₄]₂[Zn₆I₆(AsSiMe₃)₄(thf)₂] · C₆H₆ ( 11 ).