[{(CH3)3Si}3C–Li–C{Si(CH3)3}3][Li · 3(OC4H8)] und {(CH3)3Si}3C–Li · O=C(Si(CH3)3)2, zwei neue Addukte des Lithium‐trisylmethanids

[{(CH₃)₃Si}₃C–Li–C{Si(CH₃)₃}₃][Li · 3(OC₄H₈)] and {(CH₃)₃Si}₃C–Li · O=C(Si(CH₃)₃)₂, two New Adducts of Lithium Trisylmethanide Sublimation of (Tsi–Li) · 2 THF (Tsi = –C(Si(CH₃)₃)₃) at 180 °C and 10^–4 hPa gives (Tsi–Li) · 1.5 THF in very low yield. The X‐ray structure determination shows an almost linear [Tsi–Li–Tsi]^– anion connected by short agostic Li…C contacts with the threefold THF‐coordinated Li‐cation. Base‐free Tsi–Li, solved in toluene is decomposed by oxygen, forming the strawberry‐colored ketone O=C(SiMe₃)₂, which forms an 1 : 1 adduct with undecomposed Tsi–Li. The X‐ray structure elucidation of this compound is also discussed.     

Die Kristallstruktur von [Li · 11/3 H2O · C7H8][{(CH3)3Si}3C–GaI3], ein stabiles Hydrat des Lithium‐Tris(trimethylsilyl)methyl‐triiodogallats

The Crystal Structure of [Li · 1¹/₃ H₂O · C₇H₈][{(CH₃)₃Si}₃C–GaI₃], a Stable Hydrate of Lithium Tris(trimethylsilyl)methyl Triiodogallate Water‐free Li[Tsi–GaI₃], prepared from gallium triiodide and base‐free Tsi–Li (Tsi = –C(SiMe₃)₃) in toluene, which has been recrystallized several times from humid toluene, c‐hexane, benzene and toluene again gives the water‐containing title compound. According to the X‐ray structure determination this product crystallizes in the monoclinic space group P2₁/c and consists of three‐membered units of [Tsi–GaI₃]^–‐anions forming an asymmetric triangle and a related chain of three Li cations, four fold but dissimilar coordinated by the oxygen atoms of 4 water molecules, the iodligands of different anions and a h²‐bonded toluene molecule, respectively.     

Kristallstrukturen von TMEDA‐Addukten und Salzen mit protonierten TMEDA‐Molekülen

Crystal Structures of TMEDA Adducts and of Salts with Protonated TMEDA Molecules The reaction of TMEDA with two equivalents of [BH₃(SMe₂)] in toluene at 20 °C gives the adduct [TMEDA(BH₃)₂] ( 1 ). A similar reaction of pyrrolidine with [BH₃(SMe₂)] in a molar ratio of 1:1 leads to the adduct [pyrrolidine(BH₃)] ( 2 ). TMEDA can be introduced into the coordination sphere of In³⁺ by the treatment of InI₃ with TMEDA in toluene to give the complex [InI(TMEDA)] ( 3 ). The salt [HTMEDA]I ( 4 ), containing a mono‐protonated TMEDA molecule, is the result of the reprotonation of [NH₄]I and TMEDA in toluene at 20 °C. The salts [H₂TMEDA]—[InCl₄(TMEDA)]₂ ( 5 ) and [H₂TMEDA][InCl₅(THF)] ( 6 ) are formed in the reaction mixtures TMEDA/toluene/InCl₃/HCl and TMEDA/toluene/THF/InCl₃/HCl, respectively, whereupon 6 was characterized more closely. Crystals of [In₅I₆(OH)(TMEDA)₄]I·2, 5toluene ( 7 ·2.5toluene) can be obtained after treatment of InI₃ with non‐dried TMEDA; 4 was identifed as by‐product. 1 — 7 ·2.5toluene were partially investigated by NMR methods and vibrational spectroscopy. In all cases a characterization by single crystal X‐ray diffraction was performed. According to this, all nitrogen atoms in 1 and 2 are coordinated by BH₃ groups leading to a distorted tetrahedral environment at the nitrogen and the boron atoms. In 3 a distorted trigonal‐bipyramidal coordination sphere at the In³⁺ is present. The apical positions are occupied by I3 and N3. Strong N‐H···N bridges, running along [001] is the feature in 4 ; the ^I—‐Ions are not involved into the system of H‐bridges. A ion triple, [H₂TMEDA][InCl₄(TMEDA)]₂, hold together by bifurcated H‐bridges is the dominating structural motif in 5 , whereas alternation bifurcated and linear H‐bridges, leading zu a zig‐zag chain along [100], is the build‐up principle of 6 . In 7 ·2.5toluene a complex In₅O₈ skeleton was formed, consisting of a virtual corner‐connected doubled heterocubane. At every heterocubane a corner, occupied by a metal ion, is missing. The coordination spheres of the In atoms of the complex cation are completed by TMEDA molecules and iodide ions.     

Aryl- und Arin-Komplexe von Übergangsmetallen der sechsten Gruppe Darstellung von [Mo(p-C6H4CH3)6(Li · OC4H10)3] und [W(p-C6H4CH3)4(C6H3CH3)2(Li · OC4H10)4] sowie NMR-spektroskopische Untersuchung des W-Komplexes

Aryl and Aryne Complexes of Group Six Transition Metals. Preparation of [Mo(p-C₆H₄CH₃)₆(Li · OC₄H₁₀)₃] und [W(p-C₆H₄CH₃)₄(C₆H₃CH₃)₂(Li · OC₄H₁₀)₄] and NMR Spectroscopic Investigation of the W Complex Molybdenum(V) chloride reacts with an etheral solution of p-tolyllithium (molar ratio 1:10) to yield a yellow, strongly paramagnetic hexatolylo complex ([MoTol₆(Li · S)₃]¹) (μ_eff = 3.51 B.M.), while from tungsten(V) bromide and p-tolyllithium (molar ratio 1:11) a blackish violet, diamagnetic complex [WTol₄Tn₂(Li · S)₄] is formed, containing two tolylene or tolyne groups for ligands. The ¹H-NMR spectrum points to the Tol-ligands being influenced by the methyl groups of the Tn-ligands.     

Benzyl-tris(trimethylsilyl)methylzinndihalogenide, {(CH3)3Si}3C(C6H5–CH2)SnHal2 mit Hal = Cl,Br, I

Benzyl-tris(trimethylsilyl)methyl Tin Dihalides, {(CH₃)₃Si}₃C(C₆H₅–CH₂)SnHal₂ with Hal = Cl, Br, I The tin tetrahalides SnHal₄ (Hal = Cl, Br, I) react with base-free tris(trimethylsilyl)methyllithium (Tsi–Li) solved in toluene to form the trihalides Tsi–SnHal₃. But when the reaction is carried out in a 1 : 2 molar ratio at 60 °C in toluene, Tsi–H, Tsi–Hal and benzyl-trisyl tin-dihalides are formed in good yields, respectively. The nmr (¹H, ¹³C, ²⁹Si, ¹¹⁹Sn) and the Raman spectra are discussed, the X-ray structure analyses of the dibromide as well as the diiodide have been measured.     

1, 3, 4, 4'‐Tetra(triphenylphosphanimin)‐2‐iodo‐2‐butenal‐4‐carboniumiodid, [O=C(NPPh3)C(I)=C(NPPh3)‐C(NPPh3)2]+I‐

Pale yellow single crystals of [O=C(NPPh₃)C(I)=C(NPPh₃)‐C(NPPh₃)₂]⁺I^‐·1.5 thf ( 1 ·1.5 thf) have been obtained by the reaction of INPPh₃ with thallium in thf suspension. They are characterized by IR spectroscopy and by a crystal structure determination. 1 ·1.5 thf crystallizes in the monoclinic space group P2₁/n, Z = 4, lattice dimensions at ‐83?C: a = 1101.7(1), b = 3449.0(2), c = 2000.4(1) pm, β = 104.88(1)?, R₁ = 0.0382. 1 can be understood as a cationic variation of (Z)‐2‐butenale in which all H atoms are substituted by triphenylphosphoraneimine residues and by a iodine atom, respectively.     

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.     

Bildung und Molekülstruktur von [{(CH3)3Si}3C(nC3H7)In(μ‐OH)]3

Formation and Structure of [{(CH₃)₃Si}₃C(ⁿC₃H₇)In(μ‐OH)]₃ The title compound has been prepared in low yield by the reaction of [(THF)₂LiC(SiMe₃)₃]₂with humid di(n‐propyl) indium bromide and purified by sublimation at 110–115 °C/10^–3 hPa. This organo indium hydroxo compound forms a trimer via In–OH–In bridges and crystallizes in the triclinic space group P 1 with two trimers and one toluene molecule per unitcell. The In₃O₃ heterocycle has chair‐, the n‐propyl ligand has trans‐conformation, respectively.     

Heterobimetallische Komplexe von Lithium,Aluminium und Gold mit dem N‐[2‐N′,N′‐(Dimethylaminoethyl)‐N‐methyl‐aminoethyl]‐ferrocenyl‐Liganden (η5‐C5H5)Fe{η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2}

Heterobimetallic Complexes of Lithium, Aluminum, and Gold with the N ‐[2‐ N ′, N ′‐(dimethylaminoethyl)‐ N ‐methyl‐aminoethyl]‐ferrocenyl Ligand (η⁵‐C₅H₅)Fe{η⁵‐C₅H₃[CH(CH₃)N(CH₃)CH₂CH₂NMe₂]‐2} N‐[2‐N′,N′‐(dimethylaminoethyl)‐N‐methyl‐aminoethyl]ferrocene FcN,NH ( 1 ) reacts with ⁿBuLi under formation of the lithium organyl (FcN,N)Li ( 2 ). At reactions of 2 with AlBr₃ and AuCl · PPh₃ the heterobimetallic organo derivatives (FcN,N)AlBr₂ ( 3 ), (FcN,N)Au · PPh₃ ( 4 ) are formed. A detailed characterization of 2 – 4 was carried out by single crystal x‐ray analyses as well as by NMR and Mößbauer spectroscopy.     

Ein lamellarer Schichtverband auf der Grundlage von Wasserstoffbrücken und π‐Stapelung: Kristallstruktur des Lithiumkomplexes [Li{C6H4(SO2)2N}(H2O)3] und ein Vergleich mit anderen Metall(I)‐benzol‐1, 2‐di(sulfonyl)amiden

The title complex, obtained by treating ortho‐benzenedisulfonimide (HZ) with LiOH in aqueous solution, has been characterized by low‐temperature X‐ray diffraction (triclinic, space group P&1macr;, Z' = 1). The lithium cation is bonded to one sulfonyl oxygen atom and three water molecules in a distorted tetrahedral configuration [Li‐O 189.3(3)‐201.2(3) pm, O‐Li‐O 98.5(2)‐123.2(2)?]. The zero‐dimensional [Li(Z)(H₂O)₃] complexes, which display an intramolecular O(W)‐H···O hydrogen bond, are cross‐linked via five O(W)‐H···O/N/O(W) interactions and a remarkably short C‐H···O bond (H···O 217 pm, C‐H···O 170?) to form a two‐dimensional assembly comprising an internal polar lamella of metal cations, (SO₂)₂N groups and water molecules, and hydrophobic peripheral regions consisting of protruding benzo groups. In the packing, alternate carbocycles drawn from adjacent layers set up a π‐stacking array of parallel aromatic rings (intercentroid distances 349 and 369 pm, cycle spacings 331 and 336 pm). In a short survey, the currently known crystal packings of seven M^IZ · n H₂O (n ≥ 0) complexes are examined and compared.     

Darstellung,Kristallstruktur, thermischer Abbau und Schwingungsspektren von [Co(NH3)6]2[Be4O(CO3)6] · 10 H2O

Preparation, Crystal Structure, Thermal Decomposition, and Vibrational Spectra of [Co(NH₃)₆]₂[Be₄O(CO₃)₆] · 10 H₂O [Co(NH₃)₆]₂[Be₄O(CO₃)₆] · 10 H₂O is a suitable compound for the quantitative determination of beryllium. It can be obtained by reaction of aqueous solutions of carbonatoberyllate with [Co(NH₃)₆]Cl₃. The crystal structure (trigonal‐rhombohedral, R3c (Nr. 161), a = 1071,6(1) pm, c = 5549,4(9) pm, V_EZ = 5519(1) · 10⁶ pm³, Z = 6, R1(I ≥ 2σ(I)) = 0,037, wR2(I ≥ 2σ(I)) = 0,094) contains [Co(NH₃)₆]³⁺‐ and [Be₄O(CO₃)₆]^6–‐ions, which are directly hydrogen bonded as well as with water molecules. The complex cations and anions occupy the positions of a distorted anti‐CaF₂‐type. The thermal decomposition, IR and Raman spectra are presented and discussed.     

Die Reaktionen von M[BF4] (M = Li,K) und (C2H5)2O·BF3 mit (CH3)3SiCN. Bildung von M[BFx>(CN)4—x] (M = Li,K; x = 1, 2) und (CH3)3SiNCBFx(CN)3—x, (x = 0, 1)

The Reactions of M[BF₄] (M = Li, K) and (C₂H₅)₂O·BF₃ with (CH₃)₃SiCN. Formation of M[BF_x(CN)_4—x] (M = Li, K; x = 1, 2) and (CH₃)₃SiNCBF_x(CN)_3—x, (x = 0, 1) The reaction of M[BF₄] (M = Li, K) with (CH₃)₃SiCN leads selectively, depending on the reaction time and temperature, to the mixed cyanofluoroborates M[BF_x(CN)_4—x] (x = 1, 2; M = Li, K). By using (C₂H₅)₂O·BF₃ the synthesis yields the compounds (CH₃)₃SiNCBF_x(CN)_3—x x = 0, 1. The products are characterized by vibrational and NMR‐spectroscopy, as well as by X‐ray diffraction of single‐crystals: Li[BF₂(CN)₂]·2Me₃SiCN Cmc2₁, a = 24.0851(5), b = 12.8829(3), c = 18.9139(5) Å V = 5868.7(2) ų, Z = 12, R₁ = 4.7%; K[BF₂(CN)₂] P4₁2₁2, a = 13.1596(3), c = 38.4183(8) Å, V = 6653.1(3) ų, Z = 48, R₁ = 2.5%; K[BF(CN)₃] P1¯, a = 6.519(1), b = 7.319(1), c = 7.633(2) Å, α = 68.02(3), β = 74.70(3), γ = 89.09(3)°, V = 324.3(1) ų, Z = 2, R₁ = 3.6%; Me₃SiNCBF(CN)₂ Pbca, a = 9.1838(6), b = 13.3094(8), c = 16.840(1) Å, V = 2058.4(2) ų, Z = 8, R₁ = 4.4%     

Die Kristallstrukturen der Hexachlorometallate NH4[SbCl6], NH4[WCl6], [K(18‐Krone‐6)(CH2Cl2)]2[WCl6]·6CH2Cl2 und (PPh4)2[WCl6]·4CH3CN

Crystal Structures of the Hexachlorometalates NH₄[SbCl₆], NH₄[WCl₆], [K(18‐crown‐6)(CH₂Cl₂)]₂[WCl₆]·6CH₂Cl₂ and (PPh₄)₂[WCl₆]·4CH₃CN The crystal structures of the title compounds were determined by single crystal X‐ray methods. NH₄[SbCl₆] and NH₄[WCl₆] crystallize isotypically in the space group C2/c with four formula units per unit cell. The NH₄⁺ ions occupy a twofold crystallographic axis, whereas the metal atoms of the [MCl₆]^— ions occupy a centre of inversion. There exist weak interionic hydrogen bridges. [K(18‐crown‐6)(CH₂Cl₂)]₂[WCl₆]·6CH₂Cl₂ crystallizes in the orthorhombic space group R3¯/m with Z = 3. The compound forms centrosymmetric ion triples, in which the potassium ions are coordinated with a WCl₃ face each. In trans‐position to it the chlorine atom of a CH₂Cl₂ molecule is coordinated so that, together with the oxygen atoms of the crown ether, coordination number 10 is achieved. (PPh₄)₂[WCl₆]·4CH₃CN crystallizes in the monoclinic space group P2₁/c with Z = 4. This compound, too, forms centrosymmetric ion triples, in which in addition the acetonitrile molecules are connected with the [WCl₆]^2— ion via weak C—H···Cl contacts.     

Functionalization of [Ge9] with Small Silanes:[Ge9(SiR3)3]– (R = iBu,iPr, Et) and the Structures of (CuNHCDipp)[Ge9{Si(iBu)3}3], (K‐18c6)Au[Ge9{Si(iBu)3}3]2, and (K‐18c6)2[Ge9{Si(iBu)3}2]

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 CuNHC^DippCl and Au(PPh₃)Cl result in formation of the neutral metal complex (CuNHC^Dipp)[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.     

Two novel bis­(2,9‐dimeth­yl‐1,10‐phenanthroline)copper(I) complexes: [Cu(dmp)2]2(PF6)2·0.5(bpmh)·CH3CN and [Cu(dmp)2][N(CN)2]

Two new salts of the cation [Cu^I(dmp)₂]⁺ (dmp is 2,9‐dimeth­yl‐1,10‐phenanthroline, C₁₄H₁₂N₂), namely bis­[bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ²N,N′)copper(I)] bis­(hexa­fluorophos­phate) hemi[bis­(4‐pyridylmethyl­idene)hydrazine] acetonitrile solvate, [Cu(C₁₄H₁₂N₂)₂]₂(PF₆)₂·0.5C₁₂H₁₀N₄·C₂H₃N or [Cu(dmp)₂]₂(PF₆)₂·0.5(bpmh)·CH₃CN [bpmh is bis­(4‐pyridylmethyl­idene)hydrazine, C₁₂H₁₀N₄], (I), and bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ²N,N′)copper(I) dicyanamide, [Cu(C₁₄H₁₂N₂)₂](C₂N₃) or [Cu(dmp)₂][N(CN)₂], (II), are reported. The Cu—N bond lengths and the distortion from idealized tetra­hedral geometry of the dmp ligands are discussed and compared with related compounds. The bpmh molecule in (I) is π–π stacked with a dmp ligand at a distance of 3.4 Å, rather than coordinated to the metal atom. The molecule lies across an inversion center in the crystal. In (II), the normally coordinated dicyanamide mol­ecule is present as an uncoordinated counter‐ion.     

Attempted Abstraction of the Halogenides in (HNEt3)[Re(CH3CN)2Cl4] and Crystal Structures of cis‐[Re(CH3CN)2Cl4]·CH3CN and cis‐[Re(NHC(OCH3)CH3)2Cl4]

The abstraction of the halogenide ligands in [Re(CH₃CN)₂Cl₄]^? should result in a solvent‐only stabilized Re^III complex. The reactions of salts of [Re(CH₃CN)₂Cl₄]^? with silver(I) and thallium(I) salts were investigated and the solid‐state structures of cis‐[Re(CH₃CN)₂Cl₄]·CH₃CN and cis‐[Re(NHC(OCH₃)CH₃)₂Cl₄] are described.     

Syntheses and Spectroscopic Study of Some New N‐4‐Fluorobenzoyl Phosphoric Triamides; Crystal Structures of 4‐F‐C6H4C(O)N(H)P(O)R2, R = NH‐C(CH3)3, NH‐CH2C6H5, N(CH3)(CH2C6H5)

Some new N‐4‐Fluorobenzoyl phosphoric triamides with formula 4‐F‐C₆H₄C(O)N(H)P(O)X₂, X = NH‐C(CH₃)₃ ( 1 ), NH‐CH₂‐CH=CH₂ ( 2 ), NH‐CH₂C₆H₅ ( 3 ), N(CH₃)(C₆H₅) ( 4 ), NH‐CH(CH₃)(C₆H₅) ( 5 ) were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR and Mass spectroscopy and elemental analysis. The structures of compounds 1 , 3 and 4 were investigated by X‐ray crystallography. The P=O and C=O bonds in these compounds are anti. Compounds 1 and 3 form one dimensional polymeric chain produced by intra‐ and intermolecular ‐P=O···H‐N‐ hydrogen bonds. Compound 4 forms only a centrosymmetric dimer in the crystalline lattice via two equal ‐P=O···H‐N‐ hydrogen bonds. ¹H and ¹³C NMR spectra show two series of signals for the two amine groups in compound 1 . This is also observed for the two α‐methylbenzylamine groups in 5 due to the presence of chiral carbon atom in molecule. ¹³C NMR spectrum of compound 4 shows that ²J(P,C_aliphatic) coupling constant for CH₂ group is greater than for CH₃ in agreement with our previous study. Mass spectra of compounds 1 ‐ 3 (containing 4‐F‐C₆H₄C(O)N(H)P(O) moiety) indicate the fragments of amidophosphoric acid and 4‐F‐C₆H₄CN⁺ that formed in a pseudo McLafferty rearrangement pathway. Also, the fragments of aliphatic amines have high intensity in mass spectra.     

Synthesis,Characterization, and Reactivity of Cationic Palladium(II) and Platinum(II) Iodo Complexes Containing a Linear or a Tripodal Aminophosphine. The X‐Ray Crystal Structures of [Pd{HN(CH2CH2PPh2)2}I]I and [Pd3{N(CH2CH2PPh2}3)2I4]I2

The complexes [M(PNHP)I]I (PNHP = bis[2‐(diphenylphosphino)ethyl]amine; M = Pd ( 1 ), Pt ( 2 )) and [M(NP₃)I]I (NP₃ = tris[2‐(diphenylphosphino)ethyl]amine; M = Pd ( 3 ), Pt ( 4 )) were prepared by interaction of the appropriate aminophosphine in CH₂Cl₂ with aqueous solutions containing [MCl₄]^2— salts and NaI in a ratio 1:4. Complexes 2 and 3 form the polynuclear compounds [Pt₂(PNHP)₃]I₄ ( 2a ) and [Pd₃(NP₃)₂I₄]I₂ ( 3a ) in the presence of coordinating solvents such as the mixture CD₃OD/D₂O/DMSO‐d₆ and CH₂Cl₂/CH₃OH, respectively. Complex 1 consists of distorted square‐planar cations [Pd(PNHP)I]⁺ and iodide anions able to establish short N‐H···I interactions of 2.850Å. The aminophosphine adopts a boat conformation and is coordinated to palladium in a tridentate chelating fashion. The crystal structure for cations of 3a reveals the presence of two types of distorted square‐planar Pd^II atoms, PdNP₂I and trans‐PdP₂I₂, NP₃ acting as tridentate chelating and bridging ligand, respectively. On the basis of ³¹P {¹H} NMR data it has been shown that each distorted square‐planar Pt(II) centre of 2a contains one PNHP acting as tridentate chelating ligand with the other aminophosphine bridging the two metals via the P atoms. Complexes 3 and 4 were shown by ³¹P {¹H} NMR to have the metal atom bound to the three P atoms of NP₃ and one iodo ligand. Additions of AcCysSH and GSH to 4 result, by a ring‐opening process, in the formation of [Pt(NP₂PO)(SR)] (RS = Acys ( 4a ), GS ( 4b )) in which the ligand contains a dangling arm phosphine oxide group and the platinum atom achieves the four‐coordination involving the N atom of the aminophosphine. Compounds [Pt₂(PNHP)₃]Cl₄ ( 2a′ , 2a″ ), [PtAu(PNHP)₂I]I₂ ( 2b ), and [Pt(PNHP)(ONO₂)](NO₃) ( 2c ) were detected in some extent in solution by reaction of complex 2 with Au(tdg)Cl (tdg = thiodiglycol), AuI and excess AgNO₃, respectively. While 1 does not react with AuI, complex 3 affords the heterobimetallic complexes PdCu(NP₃)I₃ ( 5 ), PdAg₂(NP₃)I₄ ( 6 ) and PdAu(NP₃)I₃ ( 7 ) by interaction with the appropriate iodide M′I (M′ = Cu, Ag, Au) via a chelate ring‐opening.     

Poly[tetra‐μ2‐l‐lactato‐indium(III)sodium(I)]

The asymmetric unit of the title compound, [InNa(C₃H₅O₃)₄]_n, consists of one In^III ion, one Na^I ion and four crystallographically independent l ‐lactate monoanions. The coordination of the In^III ion is composed of five carboxylate O and two hydroxy O atoms in a distorted pentagonal–bipyramidal coordination geometry. The Na^I ion is six‐coordinated by four carboxylate O atoms and two hydroxy O atoms from four l ‐lactate ligands in a distorted octahedral geometry. Each In^III ion is coordinated by four surrounding l ‐lactate ligands to form an [In(l ‐lactate)₄]⁻ unit, which is further linked by Na^I ions through Na—O bonds to give a two‐dimensional layered structure. Hydrogen bonds between the hydroxy groups and carboxylate O atoms are observed between neighbouring layers.     

Darstellung und Strukturaufklärung von Ammonium‐tetraamminlithium‐amidotrithiophosphat‐Ammoniak(1/1) (NH4) [Li(NH3)4] [P(NH2)S3] · NH3

Synthesis and Crystal Structure of Ammonium Tetraamminelithium Amidotrithiophosphate‐Ammonia(1/1)(NH₄)[Li(NH₃)₄][P(NH₂)S₃]·NH₃ Colourless crystals of (NH₄)[Li(NH₃)₄][P(NH₂)S₃]·NH₃ were prepared by the reduction of P₄S₁₀ with a solution of lithium in liquid ammonia. The X‐ray structure determination shows them to contain the pseudo‐tetrahedral amidotrithiophosphate anion [P(NH₂)S₃]²⁻ (point group C_S), which is the hitherto unknown final member of a series of previously characterized amidothiophosphates. The ammonium ion and the ammonia molecule of solvation form an diamminehydrogen(1+)‐ion N₂H₇⁺ with a short, nearly linear hydrogen bond of 2.864(3) Å.