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.     

Reactions of tBu2P–PLi–PtBu2 with [(Et3P)2MCl2] (M = Ni,Pd, Pt). Synthesis and Properties of [(1,2‐η‐tBu2P=P–PtBu2)M(PEt3)Cl] (M=Ni,Pd)

^tBu₂P–PLi–P^tBu₂·2THF reacts with [cis‐(Et₃P)₂MCl₂] (M = Ni, Pd) yielding [(1,2‐η‐^tBu₂P=P–P^tBu₂)Ni(PEt₃)Cl] and [(1,2‐η‐^tBu₂P=P–P^tBu2)Pd(PEt₃)Cl], respectively. ^tBu₂P– PLi–P^tBu₂ undergoes an oxidation process and the ^tBu₂P–P–P^tBu₂ ligand adopts in the products the structure of a side‐on bonded 1,1‐di‐tert‐butyl‐2‐(di‐tert‐butylphosphino)diphosphenium cation with a short P–P bond. Surprisingly, the reaction of ^tBu₂P–PLi–P^tBu₂·2THF with [cis‐(Et₃P)₂PtCl₂] does not yield [(1,2‐η‐^tBu₂P=P–P^tBu₂)Pt(PEt₃)Cl].     

Synthesis,Spectroscopic, and X‐Ray Diffraction Studies of cis‐Dichlorobis(4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl3 H‐pyrazol‐3‐onato) Tin(IV)

Reaction between an aqueous ethanol solution of tin(II) chloride and that of 4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl‐3 H‐pyrazol‐3‐one in the presence of O₂ gave the compound cis‐dichlorobis(4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl‐3 H‐pyrazol‐3‐onato) tin(IV) [(C₂₆H₂₆N₄O₄)SnCl₂]. The compound has a six‐coordinated Sn^IV centre in a distorted octahedral configuration with two chloro ligands in cis position. The tin atom is also at a pseudo two‐fold axis of inversion for both the ligand anions and the two cis‐chloro ligands. The orange compound crystallizes in the triclinic space group P 1 with unit cell dimensions, a = 8.741(3) Å, b = 12.325(7) Å, c = 13.922(7) Å; α = 71.59(4), β = 79.39(3), γ = 75.18(4); Z = 2 and D_x = 1.575 g cm^–3. The important bond distances in the chelate ring are Sn–O [2.041 to 2.103 Å], Sn–Cl [2.347 to 2.351 Å], C–O [1.261 to 1.289 Å] and C–C [1.401 Å] the bond angles are O–Sn–O 82.6 to 87.7° and Cl–Sn–Cl 97.59°. The UV, IR, ¹H NMR and ¹¹⁹Sn Mössbauer spectral data of the compound are reported and discussed.     

Synthese und Charakterisierung der Siloxialane [H2AlOSiMe3]n und [HAl(OtBu)(OSiMe3)]2 sowie Redoxreaktionen von [H2AlOSiMe3]n und [H2AlOtBu]2 mit einem Zinn(II)‐amid

Synthesis and Characterisation of the Siloxialanes [H₂AlOSiMe₃]_n and [HAl(O^tBu)(OSiMe₃)]₂ as well as the Use of [H₂AlOSiMe₃]_n and [H₂AlO^tBu]₂ as Reducing Agents for a Tin(II) Amide Following the synthesis of [H₂AlO^tBu]₂ ( 1 ) and [HAl(O^tBu)₂]₂ ( 2 ) the siloxialane [H₂AlOSiMe₃]_n ( 3 ) was synthesized and has been subject to single crystal X‐ray analysis for the first time. The molecule 3 is tetrameric (n = 4) in solution and polymeric (n = ∞) in the solid state. 3 is also obtained together with the siloxide [Al(OSiMe₃)₃]₂ ( 5 ) by the reaction of the aluminiumhydride with the double molar amount of trimethylsilanol. The expected monohydride [HAl(OSiMe₃)₂]₂ ( 4 ) was not formed. The heteroleptic monohydride [HAl(O^tBu)(OSiMe₃)]₂ ( 6 ) was synthesized by the reaction of 3 with an equimolar amount of tert‐butanol and was also generated by the addition of trimethylsilanol to an equimolar amount of the alkoxialane [H₂AlO^tBu]₂ ( 1 ). Compound 6 was characterized by single crystal X‐ray diffraction analysis. Additionally we investigated the reducing force of the dihydrides 1 and 3 towards the cyclic diazastannylene Me₂Si(N^tBu)₂Sn ( 7 ). In the course of this reaction Sn^II in 7 was reduced to elementary tin whereas the hydrides were oxidized to hydrogene. Tin is obtained in its β‐form as found by powder‐X‐ray diffraction. The shapes of the metal precipitates (porous, sponge‐like pieces or nanoscaled powders) depend on the conditions of reactions. Besides the elements the spirocyclic aminoalkoxialane [Me₂Si(N^tBu)₂AlO^tBu]₂ ( 8 ) or aminosiloxialane [Me₂Si(N^tBu)₂AlOSiMe₃]₂ ( 9 ) are formed. Structural details of the molecules 8 and 9 can be derived from single crystal X‐ray analyses.     

Nitrides with Inverse K2[NiF4] Structure: (R1–xCa3+xN1–x/3)Bi2 with R = Rare‐Earth Metal

The novel nitrides (R_1–xCa_3+xN_1–x/3)Bi₂ (with R = La, Ce, Pr) crystallize in the K₂[NiF₄] structure type (I4/mmm, No. 139, Z = 2). Samples (La_1–xCa_3+xN_1–x/3)Bi₂ with x = 0.10, 0.05, 0.00, (Ce_1–xCa_3+xN_1–x/3)Bi₂ with x = 0.30, and (PrCa₃N)Bi₂ were obtained as single phase microcrystalline powders according to X‐ray diffraction and the crystal structure details were derived from Rietveld refinements based on X‐ray and neutron diffraction powder patterns. A partial order of R³⁺/Ca²⁺ on two crystallographic sites is governed by different ionic radii and charges. (La_1–xCa_3+xN_1–x/3)Bi₂ and (Ce_1–xCa_3+xN_1–x/3)Bi₂ exhibit small homogeneity ranges and typically a nitrogen deficiency. In contrast, for (PrCa₃N)Bi₂ no indications for a significant homogeneity range or deficiency of nitrogen was observed. (La_1–xCa_3+xN_1–x/3)Bi₂ with x = 0.05 is a diamagnet. X‐ray absorption spectroscopy at the CeL₃‐edge as well as magnetic susceptibility measurements evidence that (Ce_1–xCa_3+xN_1–x/3)Bi₂ with x = 0.30 contains Ce³⁺ in the 4f¹ configuration. According to electrical resistivity data, samples from all three systems are heavily doped semiconductors.     

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.     

Der Dihydridoiridium(III)‐Komplex [IrH2Cl(PiPr3)2] als Molekülbaustein für unsymmetrische Rhodium–Iridiumund Iridium–Iridium‐Zweikernverbindungen

The Dihydridoiridium(III) Complex [IrH₂Cl(P i Pr₃)₂] as a Molecular Building Block for Unsymmetrical Binuclear Rhodium–Iridium and Iridium–Iridium Compounds The title compound [IrH₂Cl(PiPr₃)₂] ( 3 ) reacts with the chloro‐bridged dimers [RhCl(PiPr₃)₂]₂ ( 1 ) and [IrCl(C₈H₁₄)(PiPr₃)]₂ ( 5 ) by cleavage of the Cl‐bridges to give the unsymmetrical binuclear complexes 4 and 6 with Rh(μ‐Cl)₂Ir and Ir(μ‐Cl)₂Ir as the central building block. The reactions of 3 with the bis(cyclooctene) and (1,5‐cyclooctadiene) compounds [MCl(C₈H₁₄)₂]₂ ( 7 , 8 ) and [MCl(η⁴‐C₈H₁₂)]₂ ( 9 , 10 ) (M = Rh, Ir) occur analogously and afford the rhodium(I)‐iridium(III) and iridium(I)‐iridium(III) complexes 11 – 14 in 70–80% yield. Treatment of [(η⁴‐C₈H₁₂)M(μ‐Cl)₂IrH₂(PiPr₃)₂] ( 13 , 14 ) with phenylacetylene leads to the formation of the substitution products [(η⁴‐C₈H₁₂)M(μ‐Cl)₂IrH(C≡CPh)(PiPr₃)₂] ( 15 , 16 ) without changing the central molecular core. Similarly, the compound [(η⁴‐C₈H₁₂)Rh(μ‐Br)₂IrH(C≡CPh)(PiPr₃)₂] ( 18 ) has been prepared; it was characterized by X‐ray crystallography.     

Reactive E=C(p‐p)π‐Systems. 56 [1] Attempted Preparation of PhE=C(CF3)2 by Reactions of Hexafluoroacetone with PhE(SiMe3)2 (E = As,P)

The chance to prepare sterically and inductively stabilized arsa‐ and phosphaalkenes of the type PhE=C(CF₃)₂ (E = As, P) by reacting phenyl‐bis(trimethylsilyl)‐arsane ( 1 ) and ‐phosphane ( 5 ), respectively, with hexafluoroacetone (HFA) was investigated. The insertion of the carbonyl function in one of the Si–E bonds was found to occur at temperatures between ?78 and 20 °C. The elimination of hexamethyldisiloxane, which in case of acylamides and ketones spontaneously follows the insertion and in case of RE(SiMe₃)–CR′₂(OSiMe₃) at least can be initiated by solid sodium hydroxide as catalyst, turned out to be impossible for the primary products PhE(SiMe₃)–C(CF₃)₂‐OSiMe₃ [E = As ( 2 ), P ( 6 )]. 2 and 6 were characterized by analytical (C, H) and spectroscopic methods (IR, NMR, MS).     

Synthese und Kristallstruktur des Azidoberyllats (Ph4P)2[Be(μ‐OSiMe3)(N3)2]2

Synthesis and Crystal Structure of the Azido Beryllate (Ph₄P)₂[Be(μ‐OSiMe₃)(N₃)₂]₂ (Ph₄P)₂[Be₂F₆] reacts with excess trimethylsilylazide in acetonitrile solution, accompanied by a hydrolytic side‐reaction to give the azido beryllate (Ph₄P)₂[Be(μ‐OSiMe₃)(N₃)₂]₂ ( 1 ) as colourless, non‐explosive crystals. 1 was characterized by IR spectroscopy and by single crystal X‐ray determination. 1 : Space group , Z = 1, lattice dimensions at 193 K: a = 1026.9(1), b = 1184.0(1), c = 1352.1(1) pm, α = 73.50(1)°, β = 74.35(1)°, γ = 64.66(1)°, R₁ = 0.0543. The complex anion of 1 forms centrosymmetric units with symmetry C_i via Be₂O₂ four‐membered rings with Be–O distances of 159.2(7) and 168.7(7) pm, and terminally bonded azide groups.     

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,Schwingungsspektrum und Kristallstruktur des Disiloxanato‐Chloroberyllats (Ph4P)2[Be4Cl6(OSiMe2OSiMe2O)2]

Synthesis, Vibrational Spectra, and Crystal Structure of the Disiloxanato‐chloroberyllate (Ph₄P)₂[Be₄Cl₆(OSiMe₂OSiMe₂O)₂] (Ph₄P)₂[Be₄Cl₆(OSiMe₂OSiMe₂O)₂] ( 1 ) was prepared by the reaction of (Ph₄P)₂[Be₂Cl₆] with cyclo‐hexamethyl‐trisiloxane in dichloromethane solution, forming colourless, moisture sensitive crystals, which are characterized by their vibrational spectra (IR, Raman) and by an X‐ray crystal structure determination. 1 crystallizes in the triclinic space group with Z = 1 and with the lattice dimensions at 193 K: a = 1050.0(1), b = 1248.2(1), c = 1312.5(1) pm, α = 84.37(1)°; β = 76.53(1)°; γ = 70.79(1)°; R₁ = 0.0349. 1 consists of (Ph₄P)⁺ions and centrosymmetric anions [Be₄Cl₆(OSiMe₂OSiMe₂O)₂]^2‐, in which the four beryllium atoms are connected by the terminal oxygen atoms of the (OSiMe₂OSiMe₂O)^2‐ ligands via two‐forked bonds to give Be₂O₂ four‐membered rings. The Be atoms of these units are additionally bridged by two μ‐Cl atoms. 1 is also obtained by reaction of (Ph₄P)₂[Be₂Cl₆] with Baysilon grease.     

μ‐Aqua‐penta­aqua­[μ‐3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine]­chloro­dinickel(II) trichloride trihydrate

The title compound, μ‐aqua‐1:2κ²O‐penta­aqua‐1κ²O,2κ³O‐μ‐3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine‐1κ²N¹,N⁶:2κ²N²,N³‐chloro‐1κCl‐dinickel(II) trichloride trihydrate, [Ni₂Cl(C₁₆H₁₄­N₄)(H₂O)₆]Cl₃·3H₂O, consists of two Ni^II atoms, a 3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine mol­ecule, four Cl atoms and nine water mol­ecules. The two Ni atoms are octahedrally coordinated by N and Cl atoms, and by water mol­ecules, and the three six‐membered rings, a pyridazine and two picolines, are planar to within 0.181 (3) Å. The crystal structure is stabilized by an intra‐ and intermolecular hydrogen‐bonding scheme involving water–water and water–chlorine interactions.     

The diastereoisomers 2‐[(S/R)‐2‐chloro‐3‐quinolyl]‐2‐[(R)‐1‐(4‐methoxyphenyl)ethylamino]acetonitrile at 100 K

In the structures of the two enantiopure diastereoisomers of the title compound, C₂₀H₁₈ClN₃O, which crystallize in different space groups, the molecules are very similar as far as bond distances and angles are concerned, but more substantial differences are observed in some torsion angles. The crystal structures of both molecules can be described as zigzag layers along the c axis. The packing is stabilized by hydrogen‐bond interactions of N—H...O, C—H...Cl and C—H...π types for 2‐[(R)‐2‐chloro‐3‐quinolyl]‐2‐[(R)‐1‐(4‐methoxyphenyl)ethylamino]acetonitrile, and of N—H...N, C—H...O and C—H...π types for 2‐[(S)‐2‐chloro‐3‐quinolyl]‐2‐[(R)‐1‐(4‐methoxyphenyl)ethylamino]acetonitrile, resulting in the formation of two‐ and three‐dimensional networks.     

Crystallographic report: [(η5‐C5H5)Fe(CO)2]2Ga3Cl3(OSiMe2OSiMe2O)2: a diiron complex of a tetracyclic trigallasiloxane

The structure of the penta‐metallic diiron trigallasiloxane, [(η⁵‐C₅H₅)Fe(CO)₂]₂Ga₃Cl₃(OSiMe₂ OSiMe₂O)₂, reveals two distinct gallium coordination environments and Fe? Ga bond lengths (2.3258(6) Å), consistent with bonding of the iron centres to four‐coordinate gallyl ligands. Copyright © 2004 John Wiley & Sons, Ltd.     

Kristallstruktur des Lithium‐Trimethylsilanolats [Li7(OSiMe3)7(THF)]

The lithium silanolate LiOSiMe₃ is accessible from the reaction of Me₃SiOSiMe₃ with LiMe in tetrahydrofuran. Single crystals of [Li₇(OSiMe₃)₇(THF)] were obtained from toluene at 25 °C. The structure of [Li₇(OSiMe₃)₇(THF)] (C2/c) features a capped trigonal antiprismatic arrangement of seven Li atoms. The Li atoms in [Li₇(OSiMe₃)₇(THF)] are μ₃‐bridged by seven O atoms of the silanolate ligand.     

Synthesis and Reactivity towards DIBAL‐H of Cyclo‐Siloxanes cyclo‐[R2SiOSi(Ot‐Bu)2O]2, cyclo‐(t‐BuO)2Si(OSiR2)2O,and cyclo‐R2Si[OSi(Ot‐Bu)2]2O (R = Me,Ph)

The six‐, eight‐ and twelve‐membered cyclo‐siloxanes, cyclo‐[R₂SiOSi(Ot‐Bu)₂O]₂ (R = Me ( 1 ), Ph ( 2 )), cyclo‐(t‐BuO)₂Si(OSiR₂)₂O (R = Me ( 3 ), Ph ( 4 )), cyclo‐R₂Si[OSi(Ot‐Bu)₂]₂O (R = Me ( 5 ), Ph ( 6 )) and cyclo‐[(t‐BuO)₂Si(OSiMe₂)₂O]₂ ( 3a ) were synthesized in high yields by the reaction of (t‐BuO)₂Si(OH)₂ and [(t‐BuO)₂SiOH]₂O with R₂SiCl₂ and (R₂SiCl)₂O (R = Me, Ph). Compounds 1 — 6 were characterized by solution and solid‐state ²⁹Si NMR spectroscopy, electrospray mass spectrometry and osmometric molecular weight determination. The molecular structure of 4 has been determined by single crystal X‐ray diffraction and features a six‐membered cyclo‐siloxane ring that is essentially planar. The reduction of 1 — 6 with i‐Bu₂AlH (DIBAL‐H) led to the formation of the metastable aluminosiloxane (t‐BuO)₂Si(OAli‐Bu₂)₂ ( 7 ) along with Me₂SiH₂ and Ph₂SiH₂.     

Bildung und Strukturen von [{η2‐tBu2P–P=P–PtBu2}Pt(PR3)2]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XVIII. Syntheses and Structures of [{η²‐^tBu₂P–P=P–P^tBu₂}Pt(PR₃)₂] ^tBu₂P–P=P(Me)^tBu₂ reacts with [{η²‐C₂H₄} · Pt(PR₃)₂] as well as with [{η²‐^tBu₂P–P}Pt(PR₃)₂] yielding [{η²‐^tBu₂P–P=P–P^tBu₂}Pt(PR₃)₂]; PR₃ = PMe₃ 3 a , PEtPh₂ 3 b , 1/2 dppe 3 c , PPh₃ 3 d , P(p‐Tol)₃ 3 e . All compounds are characterized by ¹H and ³¹P NMR spectra, for 3 b and 3 d also crystal structure determinations were performed. 3 b crystallizes in the triclinic space group P1 (No. 2) with a = 1212.58(7), b = 1430.74(8), c = 1629.34(11) pm, α = 77.321(6), β = 70.469(5), γ = 87.312(6)°. 3 d crystallizes in the triclinic space group P1 (No. 2) with a = 1122.60(9), b = 1355.88(11), c = 2025.11(14) pm, α = 83.824(9), β = 82.498(9), γ = 67.214(8)°.     

Reaktionen von tBu2P–P=P(Me)tBu2 mit (Et3P)2NiCl2 und [{η2‐C2H4}Ni(PEt3)2]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXIII. Reactions of ^tBu₂P–P=P(Me)^tBu₂ with (Et₃P)₂NiCl₂ and [{η²‐C₂H₄}Ni(PEt₃)₂] ^tBu₂P–P=P(Me)^tBu₂ ( 1 ) forms with (Et₃P)₂NiCl₂ ( 2 ) and Na(Nph) the [μ‐(1,3 : 2,3‐η‐^tBu₂P₄^tBu₂){Ni(PEt₃)Cl}₂] ( 3 ) as main product. Using Na/Hg instead as reducing agent the Ni⁰ compounds [{η²‐^tBu₂P–P}Ni(PEt₃)₂] ( 4 ), [{η²‐^tBu₂P–P=P–P^tBu₂}Ni(PEt₃)₂] ( 5 ) and [(Et₃P)Ni(μ‐P^tBu₂)]₂ ( 6 ) with four‐membered Ni₂P₂ ring result. [{η²‐C₂H₄}Ni(PEt₃)₂] yields with 1 also 4 . The compounds were characterized by ¹H and ³¹P{¹H} NMR investigations and 3 also by a single crystal X‐ray analysis. It crystallizes triclinic in the space group P 1 with a = 1129.4(2), b = 1256.8(3), c = 1569.5(3) pm, α = 72.44(3)°, β = 70.52(3)° and γ = 74.20(3)°.     

Die Kristallstrukturen der Cyanidofluoridoborate K[BFx(CN)4–x], x = 0–4

The crystal structure of K[BF₃(CN)] (Pbcn (Nr. 60) with a = 13.3486(15) b = 6.5239(7) c = 10.0085(11) Å, and eight formula units per unit cell) has been determined and the one of K[BF₂(CN)₂] was confirmed and improved. The different networks in the complete series of borates K[BF_x(CN)_4–x], x = 0–4 are compared and discussed.     

On the Reactivity of the Platina‐β‐diketone [Pt2{(COMe)2H}2(μ‐Cl)2] Towards Ph2PCH2CH2CH2SOxPh (x = 0, 2)

The reaction of the electronically unsaturated platina‐β‐diketone [Pt₂{(COMe)₂H}₂(μ‐Cl)₂] ( 1 ) with Ph₂PCH₂CH₂CH₂SPh ( 2 ) leads selectively to the formation of the acetyl(chlorido) platinum(II) complex (SP‐4‐3)‐[Pt(COMe)Cl(Ph₂PCH₂CH₂CH₂SPh‐κP,κS)] ( 4 ) having the γ‐phosphinofunctionalized propyl phenyl sulfide coordinated in a bidentate fashion (κP,κS). In boiling benzene complex 4 undergoes decarbonylation yielding the methyl(chlorido) platinum(II) complex (SP‐4‐3)‐[PtMeCl(Ph₂PCH₂CH₂CH₂SPh‐κP,κS)] ( 6 ). However, the reaction of 1 with the analogous γ‐diphenylphosphinofunctionalized propyl phenyl sulfone Ph₂PCH₂CH₂CH₂SO₂Ph ( 3 ) affords the acetyl(chlorido) platinum(II) complex (SP‐4‐4)‐[Pt(COMe)Cl(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)₂] ( 5 ). In boiling benzene complex 5 undergoes a CO extrusion yielding (SP‐4‐4)‐[PtMeCl(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)₂] ( 8 ) whereas in presence of 1 the formation of the carbonyl complex (SP‐4‐3)‐[PtMeCl(CO)(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)] ( 7 ) is observed. Addition of Ag[BF₄] to complex 5 leads to the formation of the cationic methyl(carbonyl) platinum(II) complex (SP‐4‐1)‐[PtMe(CO)(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)₂][BF₄] ( 9 ). All complexes were characterized by microanalysis and NMR spectroscopy (¹H, ¹³C, ³¹P) and complexes 4 and 6 additionally by single‐crystal X‐ray diffraction analyses.