Komplexchemie P-reicher Phosphane und Silylphosphane. IV. Bildung und Struktur der Chromcarbonylkomplexe des Tris(di-tert-butylphospha)heptaphosphanortricyclans, (t-Bu2P)3P7

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. IV. Formation and Structure of the Chromium Carbonyl Complexes of Tris(di-tert-butylphospha)heptaphosphanortricyclane (t-Bu₂P)₃P₇ The reaction of (t-Bu₂P)₃P₇ 1 with Cr(CO)₅ · THF in a molar ratio of 1:1 yields yellow crystals of (t-Bu₂P)₃P₇[Cr(CO)₅] 2 having the Cr(CO)₅ group coordinated to a P^b atom (basal) of the three membered ring. With a molar ratio of 1:2 compounds 2 , (t-Bu₂P)₃P₇[Cr(CO)₅]₂ 3 , (t-Bu₂P)₃P₇[Cr(CO)₅][Cr(CO)₄] 4 and (t-Bu₂P)₃P₇[Cr(CO)₄]₂ 5 were obtained. In 3 (yellow crystals) one Cr(CO)₅ group is linked to a P^b atom, the other one to an exocyclic P^exo atom. On irradiation 3 loosing one CO group generates 4 (orange red crystals) with an unchanged Cr(CO)₅ group linked to the Pb atom and a five membered chelate-like ring containing an apical Pa atom, two equatorial P^a atoms, one P^exo atom and the Cr atom of the carbonyl group. Compound 5 (orange red crystals) contains two such five membered rings. (t-Bu₂P)₃P₇[Cr(CO)₄]₃ 6 (red needles) is formed with Cr(CO)₅ · THF in a molar ratio of 1 : 1. However, even with higher amounts of Cr(CO)₅ · THF and after extended reaction times, only 6 is formed; no further Cr carbonyl group could be attached to the P skeleton. With Cr(CO)₅ · NBD in a molar ratio of 1 : 1, (t-Bu₂P)₃P₇[Cr(CO)₄] 7 is produced from 1, and 5 with a molar ratio of 2 : 1. As in 4, the Cr(CO)₄ group in 7 (orange crystals) participates in a five membered chelate-like ring. It was not possible to generate 6 from 5 with an excess of Cr(CO)₄ · NBD and with extended reaction times. The molecular structures of the compounds were identified by investigating the ³¹P[¹H] NMR spec-tra and considering especially the coordination shift, and by crystal structure determinations of 2 and 4. Compound 2 crystallizes in the space group PI (no.2) with a = 1566.2(4) pm, b = 2304.1(5) pm, c = 1563.3(4) pm,α = 95.57(3)°, β = 108.79(3)°, γ = 109.82(4)° and Z = 4 formula units in the elementary cell. Compound 4 crystallizes in the space group P 2₁ /n (no. 14) with a = 1416.6(5) pm, b = 2573.6(5) pm, c = 1352.9(4) pm,β = 99.17(5)° and Z = 4 formula units in the elementary cell.     

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).     

Die Phosphide LiR2P7, Li2RP7 (R = Me3Si,Et, iPr,iBu) und alkyliert-silylierte Heptaphosphane(3)

The Phosphides LiR₂P₇, Li₂RP₇ (R = Me₃Si, Et, iPr, iBu) as well as Mixed Alkylated and Silylated Heptaphosphanes(3) Formation and properties of LiR₂P₇ and Li₂PR₇ (R = Me₃Si, Et, iPr, iBu) and their reactions with Me₃SiCl or alkylhalides yielding mixed alkylated and silylated heptaphosphanes(3) are reported. Reactions of (Me₃Si)₃P₇ and Li₃P₇. 3 DME produce mixtures of Li(Me₃Si)₃P₇, Li₂(Me₃Si)P₇ and Li₃P₇ from which pure Li(Me₃Si)₂P₇ (s, as) can be isolated by means of an extraction with toluene. Similarly, the isomers of LiR₂P₇ (R = Et, iPr, iBu) can be extracted from the mixtures obtained by reacting Li₃P₇ with alkylbromides. The (s) isomers of LiR₂P₇ in solution at about 20°C from the (as) isomers whereas the latter up to 70°C do not show any inversion. The (as) lithiumdialkylphosphides can be obtained as ether free products (red brown powder, isoluble in toluene, soluble in THF) by repeated addition of toluene and removal of the solvents; the (s) isomers decompose during the procure. In reactions of LiEt₂P₇. THF (s, as) in toluene at ?30°C with EtBr only the (s) isomer is substituted and gives Et₃P₇ (s), however on warming to 20°C by inversion of P^e a ratio of (s) : (as( = 1 : 3 is obtained. With Li(iBu)₂P₇, (s) reaction begins above ?20°C the giving both the (s) and the (as) isomer. (iBu)₃P₇ (s) is the prefered isomer at higher temperatures. Li(Me₃Si)₂P₇ (s, as) with Me₃SiCl exclusively yields (Me₃Si)₃P₇ (s). Li₂RP₇ (R = alkyl, Me₃SI) is not available. From mixtures with LiR₂P₇ and Li₃P₇, it can be isolated only after repeated cumbersome extraction of LiR₂P₇ as was shown with Li₂(iPr)P₇ as an example. Ether free LiEt₂P₇(s, as) with Me₃SiCl exclusively gives Et₂(Me₃Si)P₇ (s, as) whereas LiEt₂P₇ ? THF due to its THF content does not. Similarly, ether free Li(iBu)₂P₇ yields (iBu)₂(Me₃Si)P₇ (s, as). The compounds R(Me₃Si)₂P₇ (R = alkyl) cannot be selectively prepared neither starting from Li₂RP₇ with Me₃SiCI) nor from Li(Me₃Si)₂P₇ with RX. Such, the reaction of Li(Me₃Si)₂P₇ ? THF with EtBr in toluene at ?78°C yield a mixture of Et(Me₃Si)₂P₇ (42%), Et₂(Me₃Si)P₇ (27010), (Me₃Si)₃P₇ (29%) and Et₃P₇ (2%). (Me₃Si)₃P₇ with MeI in a molar ratio of 1 : 1 at 70°C quantitatively produces Me(Me₃Si)₂P₇ whereas already using a molar ratio of 1 : 2 also Me₃P₇ is obtained. With EtBr mixtures of Et(Me₃Si)₂P₇ and Et₃P₇ are formed. iBuBr gives iBu₃P₇, but tBuBr does not yield any tBu₃P₇.     

Komplexchemie P-reicher Phosphane und Silylphosphane. VII [1]. Bildung und Struktur von [Li(DME)3]2{(SiMe3)[Cr(CO)5]2 P?PP?P[Cr(CO)5]2(SiMe3)}

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. VII. Formation and Structure of [Li(DME)₃]₂{(SiMe₃)[Cr(CO)₅]₂ P-P ? P-P[Cr(CO)₅]₂(SiMe₃)} Deep red crystals of the title compound 1 are produced in the reaction of LiP(Me₃Si)₂[Cr(CO)₅] with 1, 2-dibromoethane in DME. The structure of 1 was derived from the investigation of the ³¹P-NMR spectra and confirmed by a single crystal structure determination. 1 crystallizes in the space group P1 (no. 2); a = 1307.8(5)pm, b = 1373.1(5)pm, c = 1236.1(4)pm, α = 106.22(4)°, β = 88.00(3)°, γ = 115.52(4)° and Z = 1. 1 forms a salt composed of a dianion R₂R₄′P₄^2? (R ? SiMe₃, R′ ? Cr(CO)₅) and solvated Li⁺ cations. The zigzag shaped dianion possesses the symmetry 1 -C_i. The distances d(P? P) = 202.5(1)pm and d(P? P) = 221.9(1)pm correspond to a double bond and single bonds, respectively. The distances d(Cr? P) = 251.1(1) pm and 255.3(1) pm are larger than those observed so far which might be caused by the charge distribution in the dianion.     

Komplexchemie P-reicher Phosphane und Silylphosphane. VII. Carbonylkomplexe des Heptaphosphans(3) iPr2(Me3Si)P7

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. VII Carbonyl Complexes of the Heptaphosphane(3) iPr₂(Me₃Si)P₇ From the reaction of iPr₂(Me₃Si)P₇ 1 with one equivalent of Cr(CO)₅THF the yellow products iPr₂(H)P₇[Cr(CO)₅] 2 and iPr₂(Me₃Si)P₇[Cr(CO)₅] 3 were isolated by column chromatography on silicagel. The P? H group in 2 results from a cleavage of the P? SiMe₃ bond during chromatography. The Cr(CO)₅ group in 2 is linked to an iPr? P^e atom, in 3 to the Me₃Si? P^e atom of the P₇ skeleton. The substituents do not force the formation of a single isomer; nevertheless 3 ist considerably favoured as compared to 2 . From the reaction of 1 with 2 equivalents of Cr(CO)₅THF the yellow iPr₂(H)P₇[Cr(CO)₅]₂ 4 was isolated bearing one Cr(CO)₅ group at an iPr? P^e atom, the other one at a P^b atom of the P₇ skeleton. Compound 3 yields with Cr(CO)₄NBD the red iPr₂(Me₃Si)P₇[Cr(CO)₅][Cr(CO)₄] 5 . Three isomers of 5 appear. Two P^e atoms of 5 are bridged by the Cr(CO)₄ group, the third P^e atom is linked to the Cr(CO)₅ ligand. iPr₂(H)P₇[Fe(CO)₄] was isolated from the reaction of 1 with Fe₂(CO)₉. ³¹P NMR and MS data are reported.     

Komplexchemie P-reicher Phosphane und Silylphosphane. XI [1]. Bildung,Reaktionen und Strukturen von Chromcarbonylkomplexen aus Reaktionen von Li(THF)2[η2-(tBu2P)2P] mit Cr(CO)5 · THF und Cr(CO)4 · NBD

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. XI. Formation, Reactions, and Structures of Chromium Carbonyl Complexes from Reactions of Li(THF)₂[η₂-(^tBu₂P)₂P] with Cr(CO)₅ · THF and Cr(CO)₄ · NBD Reactions of Li(THF)₂[η²-(^tBu₂P)₂P] 1 with Cr(CO)₅ · THF yield Li(THF)₂Et₂O[Cr(CO)₄{η²-(^tBu₂P)₂P}η¹-Cr(CO)₅] 2 and the compounds [Cr(CO)₄{η²-(^tBu₂P)₂PH}] 3 , [Cr(CO)₅{η¹-(^tBu₂P)₂PH}] 4 , (^tBu₂P)₂PH 5 and ^tBu₂PH · Cr(CO)₅ 6 . The formation of 3, 4, 5 and 6 is due to byproducts coming from the synthesis of 1. 2 reacts with CH₃COOH under formation of 3 . After addition of 12-crown-4 1 with NBD · Cr(CO)₄ in THF forms Li(12-crown-4)₂[Cr(CO)₄-{η²-(^tBu₂P)₂P}] 7 (yellow crystals). 7 reacts with CH₃COOH to 3 – which regenerates 7 with LiBu – with Cr(CO)₅THF to compound 2 , with NBD · Cr(CO)₄ in THF to 2 and 3 (ratio 1 : 1). With EtBr, 7 forms [Cr(CO)₄{η²-(^tBu₂P)₂PEt}] 8 , and [Cr(CO)₄{η²-(^tBu₂P)₂PBr}] 9 with BrCH₂? CH₂Br. The compounds were characterized by means of ¹H, ¹³C, ³¹P, ⁷Li NMR spectroscopy, IR spectroscopy, elementary analysis, mass spectra, and 2, 3 and 4 additionally by means of X-ray diffraction analysis. 2 crystallizes in the space group P1 with 2 formula units in the elementary cell; a = 10.137(9), b = 15.295(12), c = 15.897(14) Å; α = 101.82(7), β = 91.65(7), γ = 98.99(7)°; 3 crystallizes in the space group P2_t/n with 4 molecules in the elementary unit; a = 11.914(6), b = 15.217(10), c = 14.534(10) Å; α = 90, β = 103.56(5), γ = 90°. 4 : space group P1 with 2 molecules in the elementary unit; a = 8.844(4), b = 12.291(6), c = 14.411(7) Å, α = 66.55(2), β = 89.27(2), γ = 71.44(2)°.     

Reaktionen des [η2-{P–PtBu2}Pt(PPh3)2] und [η2-{P–PtBu2}Pt(dppe)] mit Metallcarbonylen. Bildung von [η2-{(CO)5M · PPtBu2}Pt(PPh3)2] (M = Cr,W) und [η2-{(CO)5Cr · PPtBu2}Pt(dppe)]

Coordination Chemistry of P-rich Phosphanes and Silylphosphanes. XVI [1] Reactions of [g²-{P–P^tBu₂}Pt(PPh₃)₂] and [g²-{P–P^tBu₂}Pt(dppe)] with Metal Carbonyls. Formation of [g²-{(CO)₅M · PP^tBu₂}Pt(PPh₃)₂] (M = Cr, W) and [g²-{(CO)₅Cr · PP^tBu₂}Pt(dppe)] [η²-{P–P^tBu₂}Pt(PPh₃)₂] 4 reacts with M(CO)₅ · THF (M = Cr, W) by adding the M(CO)₅ group to the phosphinophosphinidene ligand yielding [η²-{(CO)₅Cr · PP^tBu₂}Pt(PPh₃)₂] 1 , or [η²-{(CO)₅W · PP^tBu₂}Pt(PPh₃)₂] 2 , respectively. Similarly, [η²-{P–P^tBu₂}Pt(dppe)] 5 yields [η²-{(CO)₅Cr · PP^tBu₂}Pt(dppe)] 3 . Compounds 1 , 2 and 3 are characterized by their ¹H- and ³¹P-NMR spectra, for 2 and 3 also crystal structure determinations were performed. 2 crystallizes in the monoclinic space group P2₁/n (no. 14) with a = 1422.7(1) pm, b = 1509.3(1) pm, c = 2262.4(2) pm, β = 103.669(9)°. 3 crystallizes in the triclinic space group P1 (no. 2) with a = 1064.55(9) pm, b = 1149.9(1) pm, c = 1693.2(1) pm, α = 88.020(8)°, β = 72.524(7)°, γ = 85.850(8)°.     

Komplexchemie at P-reicher Phosphane und Silylphosphane. VI. Bildung und Struktur der Chromcarbonylkomplexe des Tris(trimethylsilyl) heptaphosphanortricyclans (Me3Si)3P7

Formation and Structures of Chromium Carbonyl Complexes of Tris(trimethylsily)heptanortricyclane (Me₃Si)₃P₇ (Me₃Si)₃P₇ 1 reacts with one equivalent of Cr(Co)₅THF 2 to give the yellow (Me₃Si)₃P₇[Cr(Co)₅] 4. The Cr(Co)₅group is attached to a P^e atom. Yellow (Me₃Si)₃P₇[Cr(CO)₅]₂ 5 is obtained either from reacting 1 with two equivalents of 2 , or from 4 with one equivalent of 2. One Cr(CO)₅ groups in 5 is coordinated to a P^e atom, the other one to a P,^b atom. Similarly, Yellow (Me₃Si)₃P₇[Cr(CO)₅]₃ 6 results from reacting 5 with one equivalent of 2 . Two Cr(CO)₅ groups in 6 are linked to P^b atoms, and the third one either to a P^e or the P^a atom (assignment not completely clear). Derivatives containing a P^e bridge appear in reactions of 1 with higher amounts of 2 . Such, 5 forms mixtures of the red compounds (Me₃Si)₃P₇ × [Cr(CO)₅]₂[Cr(CO)₄] 8 and (Me₃Si)₃P₇[Cr(CO)₅] × [Cr(CO)₄] 9 , and even preferably 9 with four equivalents of 2 . In 8 , one Cr(CO)₅ group is attached to that p^e atom which is not engaged in the Cr(CO)₄ bridge, and the second to one of the P^b atoms directly adjacent to the bridge. The additional Cr(CO)₅ group in 9 is coordinated to the remaining P^b atom directly adjacent to the bridge. In reactions of 5 with even higher amounts of 2 , four Cr(CO)₅ groups and one Cr(CO)₄ bridge attach to the basic P₇ skeleton to from the less stable Me₃P₇[Cr(CO)₅]₄[Cr(CO)₄]. (Me₃Si)₃P₇ 1 reacts considerably slower with Cr(CO)₅THF 2 than R₃P₇ (R = Et, iPr). Cr(CO)₄NBD 3 reacts with 1 , but it was not possible to isolate (Me₃Si)₃P₇[Cr(CO)₄]. However, 4 with 3 forms (Me₃Si)₃P₇[Cr(CO)₅][Cr(CO)₄] 7 , and 5 with 3 yields (Me₃Si)₃P₇[Cr(CO)₅]₂[Cr(CO)₄] 8 . The structures of 4 , 5 , 7 , 8 or 9 are quite analogous to those of the derivatives of Et₃P₇ but there exist significant differences in stability and reactivity. While Et₃P₇[Cr(CO)₅]₂ in solution rearranges to give the stable Et₃P₇[Cr(CO)₅][Cr(CO)₄], the analogous (Me₃Si)₃P₇[Cr(CO)₅][Cr(CO)₄] 7 is not stable and is not obtained from (Me₃Si)₃P₇[Cr(CO)₅]₂ 5 . Et₃P₇[Cr(CO)5]₃ can just be detected spectroscopically and rearranges easily to give Et₃P₇[Cr(CO)₅]₂ [Cr(CO)₄] whereas (Me₃Si)₃P₇[Cr(CO)₅]₃ 6 can be isolated. These differences are caused by the greater steric requirements of Me₃Si groups. The formation of a P^e–Cr(CO)₄–P^e bridge, e.g., requires a Me₃Si group in 1 to switch from the s to the as position. Whereas many of the complex compounds of R₃P₇ (R = Et, iPr) crystallize easily, the analogous derivatives of (Me₃Si)₃P₇ did not yield crystals. The structures of the products were assigned by evaluating the coordination shift in their ₃₁P NMR spectra and by comparision of these spectra with those of such derivatives of Et₃P₇ which previously had been investigated by single crystal structure determinations.     

Zur Bildung und Struktur der Phosphinophosphiniden-phosphorane tBu2P?PP(Me)tBu2 1, tBu(Me3Si)P?PP(Me)tBu2 2 und tBu2P?PP(Br)tBu2 3

Synthesis and Structure of Phosphinophosphinidene-phosphoranes tBu₂P? P?P(Me)tBu₂ 1, tBu(Me₃Si)P? P?P(Me)tBu₂ 2, and tBu₂P? P?P(Br)tBu₂ 3 A new method for the synthesis of 1 and 2 (Formulae see ?Inhaltsübersicht”?) is reported based on the reaction of 5 with substitution reagents (Me₂SO₄ or CH₃Cl). The results of the X-ray structure determination of 1 and 2 are given and compared with those of 3 . While in 3 one P? P distance corresponds to a double bond and the other P? P distance to a single bond (difference 12.5 pm) the differences of the P? P distances in 1 and 2 are much smaller: 5.28 pm in 1 , 4.68 pm in 2 . Both 1 and 2 crystallize monoclinic in the space group P2₁/n (Z = 4). 2 additionally contains two disordered molecules of the solvent pentane in the unit cell. Parameters of 1 : a = 884.32(8) pm, b = 1 924.67(25) pm, c = 1 277.07(13) pm, β = 100.816(8)°, and of 2 : a = 1 101.93(12) pm, b = 1 712.46(18) pm, c = 1 395.81(12) pm, β = 111.159(7)°, all data collected at 143 K. The skeleton of the three P atoms is bent (PPP angle 100.95° for 1 , 100.29° for 2 and 105.77° for 3 ). Ab initio SCF calculations are used to discuss the bonding situation in the molecular skeleton of the three P atoms of 1 and 3 . The results show a significant contribution of the ionic structure R₂P? P(^?)? P(⁺)(X)R₂. The structure with (partially) charged P atoms is stabilized by bulky polarizable groups R (as tBu) as compared to the fully covalent structure R₂P? P(X)? PR₂.     

New Fluoromanganate(III) Hydrates: Mn3F8 · 12H2O and AgMnF4 · 4H2O

Single crystals of fluoride hydrates Mn₃F₈ · 12 H₂O and AgMnF₄ · 4 H₂O have been prepared and characterized by X-ray methods. Mn₃F₈ · 12 H₂O crystallizes in the space group P1 (a = 623.0(3), b = 896.7(4), c = 931.8(4) pm, α = 110.07(2)°, β = 103.18(2)°, γ = 107.54(2)°, Z = 1); AgMnF₄ · 4 H₂O crystallizes in the space group P2₁/m (a = 700.9(2), b = 726.1(1), c = 749.4(3) pm, β = 107.17(3)°, Z = 2). Both structures contain Jahn-Teller-distorted [Mn(H₂O)₂F₄]^? anions as well as crystal water molecules and exhibit a complex hydrogen bond network between anions and cations, i. e. [Mn(H₂O)₆]²⁺ for the first and a polymeric [Ag(H₂O)₂]^? cation for the second compound.     

Beiträge zur Chemie des Phosphors. 245 [1], LiP7(BNEt2)2 und P7(BNEt2)4Cl: Zwei neuartige polycyclische Boraphosphane

Contributions to the Chemistry of Phosphorus. 245, LiP₇(BNEt₂)₂ and P₇(BNEt₂)₄Cl: Two Novel Polycyclic Boraphosphanes The directed synthesis of a noval tetracyclic heteropolyphosphane skeleton from a tricyclophosphane has been achieved by condensation of Li₃P₇ · 3DME with Cl(Et₂N)B‐B(NEt₂)Cl to the diboranonaphosphanide LiP₇(BNEt₂)₂ ( 1 ). When the reaction proceeds the mixed‐substituted diboranonaphosphane P₇(BNEt₂)₄Cl ( 2 ) is formed. According to their ³¹P NMR spectra 1 and 2 possess a B₂P₇(3) skeleton analogous to that of the hydrocarbon deltacyclane. Additional weak signals in the ³¹P NMR spectrum of 2 indicate that also small amounts of the symmetrically substituted diborane(4) P₁₄B₆(NEt₂)₆ ( 3 ) are formed.     

Neutrale Thiolate und ein Iodidthiolat von Antimon(III). Die Kristallstrukturen von Sb(SC6H5)3, Sb(SC6H2Me3-2,4,6)3 und SbI(SC6H2Me3-2,4,6)2

Neutral Thiolates and a Iodothiolate of Antimony(III). Crystal Structures of Sb(SC₆H₅)₃, Sb(SC₆H₂Me₃-2,4,6)₃, and SbI(SC₆H₂Me₃-2,4,6)₂ The crystal structures of Sb(SC₆H₅)₃ ( 1 ), Sb(SC₆ · H₂Me₃-2,4,6)₃ ( 2 ), and the novel compound SbI(SC₆H₂Me₃-2,4,6)₂ ( 3 ) have been determined by X-ray crystallography. In addition to the expected trigonal pyramidal coordination of antimony intermolecular interactions are observed for 1 (Sb … O: 363.3 pm) and 3 (Sb … S: 2 × 369.4 pm) but not for 2 . The reasons for these differences are discussed.     

Clusteraufbau durch Photolyse von Azidokomplexen des Platins und Golds. Synthesen und Kristallstrukturen von [(Ph3PAu)6(AuCl)3Pt(CO)], [(dppe)PtCo2(CO)7] und [(Ph3PAu)4Pt(dppe)](PF6)2

Cluster Synthesis by Photolysis of Azido Complexes of Platinum and Gold. Syntheses and Crystal Structures of [(Ph₃PAu)₆(AuCl)₃Pt(CO)], [(dppe)PtCo₂(CO)₇] and [(Ph₃PAu)₄Pt(dppe)](PF₆)₂ Photolysis of a mixture of Ph₃PAuN₃, Ph₃PAuCl and (Ph₃P)₂Pt(N₃)₂ in THF yields after chromatographic separation with CH₂Cl₂/EtOH as eluens the cluster [(Ph₃PAu)₆(AuCl)₃Pt(CO)] ( 1 ). It crystallizes in the triclinic space group P1 with the lattice parameters a = 2 139.3(4), b = 2 457.1(4), c = 2 561.9(1) pm, α = 79.74(9)°, β = 80.06(6)°, γ = 66.05(5)°, Z = 4. The nine gold atoms form a fragment of an icosahedron with the platinum atom in its center. Upon photolysis of (dppe)Pt(N₃)₂ with Co₂(CO)₈ in THF one m?₂-CO ligand of the cobalt carbonyl is substituted by a (dppe)Pt group. The resulting cluster [(dppe)PtCo₂(CO)₇] ( 2 ) crystallizes monoclinically in the space group P2₁/n with a = 1 303.9(3), b = 1 768.1(8), c = 1 461.4(4) pm, β = 102.81(1)°, Z = 4. Photolysis of 2 with excess Ph₃PAuN₃ affords the clusters [(Ph₃PAu)₄Pt(dppe)]²⁺ ( 3 ), and [(Ph₃PAu)₆AuCo₂(CO)₆]⁺. 3 crystallizes with PF as counterions in the triclinic space group P1 with a = 1 369.1(4), b = 1 505.0(4), c = 2 773.0(8) pm, α = 84.74(1)°, β = 87.37(2)°, γ = 65.94(2)°, Z = 2. The Au₄Pt skeleton of 3 forms a trigonal bipyramid with the platinum atom in equatorial position.     

Synthese und Kristallstrukturen von (Ph4P)4[Bi8I28], (nBu4N)[Bi2I7] und (Et3PhN)2[Bi3I11] – Iodobismutate mit isolierten bzw. polymeren Anionen

Synthesis and Crystal Structures of (Ph₄P)₄[Bi₈I₂₈], (ⁿBu₄N)[Bi₂I₇], and (Et₃PhN)₂[Bi₃I₁₁] – Bismuth Iodo Complexes with Isolated and Polymeric Anions Solutions of BiI₃ in methanol react with NaI and (ⁿBu₄N)(PF₆) or (Et₃NPh)(PF₆) to form anionic bismuth iodo complexes (ⁿBu₄N)[Bi₂I₇] 1 and (Et₃PhN)₂[Bi₃I₁₁] 2 . In 1 Bi₄I₁₆ units, and in 2 Bi₆I₂₄ units are linked by common I-atoms to onedimensional infinite chains. Reaction of BiI₃ with (Ph₄P)(PF₆) in methanol yields (Ph₄P)₄[Bi₈I₂₈] 3 . The anions of 1–3 consist of edge-sharing BiI₆ octahedra. (ⁿBu₄N)[Bi₂I₇] 1 : Space group I2/m (No. 13), a = 1 082.3(5), b = 2 597.1(13), c = 1 206.1(6) pm, β = 93.17(2)°, V = 3 385(3) · 10⁶ pm³; (Et₃PhN)₂[Bi₃I₁₁] 2 : Space group P1 (No. 2), a = 1 283.5(6), b = 1 345.9(7), c = 1 546.3(8) pm, α = 83.87(2), β = 74.24(2), γ = 68.26(2)°, V = 2 388(2) · 10⁶ pm³; (Ph₄P)₄[Bi₈I₂₈] 3 : Space group P1 (No. 2), a = 1 329.3(4), b = 1 337.0(4), c = 2 193.1(5) pm, α = 104.20(2), β = 99.73(2), γ = 100.44(2)°, V = 3 622(2) · 10⁶ pm³.     

Synthese und Kristallstrukturen der Samarium-Komplexe [SmI2(DME)3] und [Sm2I(NPPh3)5(DME)]

Synthesis and Crystal Structures of the Samarium Complexes [SmI₂(DME)₃] and [Sm₂I(NPPh₃)₅(DME)] When treated with ultrasound, the reaction of samarium metal with N-iodine-triphenylphosphaneimine in 1,2-dimethoxyethane (DME) leads to the two samarium complexes [SmI₂(DME)₃] ( 1 ) and [Sm₂I(NPPh₃)₅(DME)] ( 2 ), which are separated from each other by fractional crystallization. 1 could be isolated in two different crystallographic forms, namely as brownish black crystals ( 1 a ) and as violet-black crystals ( 1 b ), both of them are characterized by crystal structure analyses. 1 a : Space group P2₁/c, Z = 4, lattice dimensions at –80 °C: a = 1459.4(1), b = 1314.4(1), c = 2293.6(2) pm, β = 99.245(8)°, R = 0.0344. The structure of 1 a holds two crystallographically independent molecules [SmI₂(DME)₃], in which the samarium atoms have coordination number eight. The two individuals differ from each other particularly in their I–Sm–I bond angles, which are 157.94 and 178.45°. 1 b : Space group P2₁, Z = 2, lattice dimensions at –80 °C: a = 849.4(3), b = 1060.1(3), c = 1235.1(6) pm, b = 93.86(5)°, R = 0.0251. 1 b has a molecular structure similar to that of 1a with a bond angle I–Sm–I of 158.40°. The phosphoraneiminato complex [Sm₂I(NPPh₃)₅(DME)] ( 2 ) forms colourless, moisture sensitive crystals which contain two molecules DME per formula unit. 2 · 2 DME: Space group P1, Z = 2, lattice dimensions at –80 °C: a = 1405.0(4), b = 1656.5(3), c = 2208.3(7) pm, α = 89.60(3)°, β = 72.96(4)°, γ = 78.70(3)°, R = 0.0408. In 2 the two samarium atoms are linked via the μ-N atoms of two phosphoraneiminato ligands to form a planar Sm₂N₂ four-membered ring. One of the Sm atoms is terminally coordinated by the N atoms of two (NPPh₃)^– groups, thus achieving a distorted tetrahedral surrounding. The second Sm atom is coordinated by the N atom of one (NPPh₃)^– group, by the terminally bonded iodine atom, and by the O atoms of the DME chelate, thus achieving a distorted octahedral surrounding.     

Azidokomplexe von Vanadium(IV) und Vanadium(V): (Ph4P)2[VOCl2(μ‐N3)]2 und (Ph4P)2[VOCl(μ‐N3)(N3)2]2

Azido Complexes of Vanadium(IV) and Vanadium(V): (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ and (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ ( 1 ) was prepared by reaction of (Ph₄P)[VO₂Cl₂] with trimethylsilylazide in the molar ratio 1:2 in dichloromethane solution to give dark green, moisture sensitive, non‐explosive single crystals. The reaction is accompanied by the formation of the dark blue side‐product (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ ( 2a ), which can be obtained as the main product by application of a large excess of Me₃SiN₃. Dark blue needles of 2a crystallize spontaneously from the CH₂Cl₂ solution within one hour at 4 °C. After standing at 4 °C under its mother liquid within 24 hours a first‐order phase transition of 2a occurs forming dark blue prismatic single crystals of 2b . According to single crystal X‐ray structure determinations, 2a and 2b crystallize in the same type of space group , however, with different lattice dimensions. The vanadium(IV) complex 1 is characterized by X‐ray structure determination and by vibrational spectroscopy (IR, Raman) as well as by EPR spectroscopy, whereas 2b is characterized by IR spectroscopy. 1 : Space group P2₁/n, Z = 2, a = 1009.5(1), b = 1226.6(2), c = 1943.0(2) pm, β = 98.42(1)°, R₁ = 0.0672. The complex anion forms centrosymmetric units with V₂N₂‐four‐membered rings with a V···V distance of 335.6(1) pm and coordination number five on the vanadium(IV) atoms. 2a : Space group , Z = 1, a = 1089.0(2), b = 1097.1(2), c = 1310.1(2) pm, α = 92.99(1)°, β = 106.12(2)°, γ = 117.05(2)°, V = 1309.8(4) ų, d_calc. = 1.440 g·cm^?3, R₁ = 0.0384. The complex anion forms centrosymmetric units of symmetry C_i with V₂N₂ four‐membered rings and VN bond lengths of 200.4(3) and 234.4(2) pm, respectively. The non‐bonding V···V distance amounts to 356.2(1) pm. 2b : Space group , Z = 1, a = 1037.3(2), b = 1157.6(2), c = 1177.2(2) pm, α = 98.48(2)°, ° = 103.82(2)°, γ = 106.33(2)°, V = 1281.8(4) ų, d_calc. = 1.471 g·cm^?3, R₁ = 0.0724. The structure of the complex anion is similar to the anion of 2a with VN bond lengths of the four‐membered V₂N₂ ring of 203.3(4) and 235.2(4) pm, respectively, and a non‐bonding V···V distance of 357.5(1) pm.     

Clusteraufbau durch Photolyse von R3PAuN3. VIII. Synthese und Kristallstruktur von [(Ph3PAu)5Mo(CO)4]PF6 · CH2Cl2 und (Ph3PAu)3Co(CO)3

Cluster Synthesis by Photolysis of R₃PAuN₃. VIII. Synthesis and Crystal Structure of [(Ph₃PAu)₅Mo(CO)₄]PF₆ · CH₂Cl₂ and (Ph₃PAu)₃Co(CO)₃ Photolysis of a mixture of Ph₂PAuN₃ and Mo(CO)₆ in THF yields [(Ph₃PAu)₅Mo(CO)₄]⁺ (1), which can be crystallized from CH₂Cl₂/diisopropylether as orange 1 · PF₆ · CH₂Cl₂ with the space group P2₁/c and a = 1681.4(5), b = 2215.6(12), c = 2761.5(9) pm, β = 91.54(3)°, Z = 4. The Au₅Mo center of cluster 1 forms a capped trigonal bipyramid with the Mo atom in equatorial position and almost equal Mo? Au distances between 279.9(5) and 284.6(7) pm to all five Au atoms. The Au? Au distances range from 272.2(4) to 301.3(4) pm. The Mo(CO)₄ group causes three v(C0) at 1975, 1915 and 1890cm^?1. Reaction of Ph₃PAuCo(CO)₄ with Ph₃PAuPF₆ affords the known cluster cation [(Ph₃PAu)₄Co(CO)₃]⁺ in high yield. It can be degraded with C1^? to the neutral cluster (Ph₃PAu)₃Co(CO)₃ (2). 2 forms air stable, yellow crystals with the space group P2₁/n and a = 1359.4(4), b = 2041.0(5), c = 1853.2(6)pm, β = 91.47(1)°, Z = 4. The Au₃Co core of 2 has a tetrahedral structure with distances Co? Au between 250.4(1) and 254.0(2) pm and Au? Au between 279.5(1) and 285.1(1) pm. v(C0) are observed at 1963, 1905 and 1891 cm^?1. Reaction of 2 with [(Ph₃PAu)₄Co(CO)₃]⁺ yields the condensed cluster [(Ph₃PAu)₆AuCo₂(CO)₆]⁺.     

Komplexchemie P-reicher Phosphane und Silylphosphane. X [1] Zum Einfluß der Komplexierung auf die Reaktivität des [(Me3Si)2P]2PH

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. X. The Influence of the Formation of Complex Compounds on the Reactivity of [(Me₃Si)₂P]₂PH Whereas [(Me₃Si)₂P]₂PH 1 by BuLi is attacked at the PH group to give [(Me₃Si)₂P]₂PLi 2 , the related chromium carbonyl complex (Me₃Si)P^IV ? ²P^IV(H) ? ³P^III(Si? Me₃)₂ · Cr(CO)₄ 3 with BuLi yields Li(Me₃Si)¹P^IV ? ²P^IV(H) ? ³P^III(SiMe₃)₂ · Cr(CO)₄ 4 by cleaving a Si? P bond at the chromium substituted ¹P atom. Dissolved in ether, 4 is stable for a longer time, while under comparable conditions 2 forms Li₃P₇ which is not obtained from 4 . MeOH in 3 cleaves selectively the Me₃Si groups from the complex substituted P atom yielding (Me₃Si)(H)¹P^IV ? ²P^IV(H) ? ³P^III(SiMe₃)₂ · Cr(CO)₄ 5 and HP^IV ? ²P^IV(H) ? ³P^III(SiMe₃)₂Cr(CO)₄ 6. 5 and 6 seem to be stable in contrast to the uncoordinated triphosphanes which are not known.     

[Co4P2(PtBu2)2(CO)8] und [{Co(CO)3}2P4tBu4] aus Co2(CO)8 und tBu2P–P=P(Me)tBu2

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XIX. [Co₄P₂(P^tBu₂)₂(CO)₈] and [{Co(CO)₃}₂P₄^tBu₄] from Co₂(CO)₈ and ^tBu₂P–P=P(Me)^tBu₂ Co₂(CO)₈ reacts with ^tBu₂P–P=P(Me)^tBu₂ yielding the compounds [Co₄P₂(P^tBu₂)₂(CO)₈] ( 1 ) and [{η^2tBu₂P=P–P=P^tBu₂}{Co(CO)₃}₂] ( 2 a ) cis, ( 2 b ) trans. In 1 , four Co and two P atoms form a tetragonal bipyramid, in which two adjacent Co atoms are μ₂‐bridged by ^tBu₂P groups. Additionally, two CO groups are linked to each Co atom. In 2 a and 2 b , each of the Co(CO)₃ units is η²‐coordinated to the terminal P₂ units resulting in the cis‐ and trans‐configurations 2 a and 2 b . 1 crystallizes in the orthorhombic space group Pnnm (No. 58) with a = 879,41(5), b = 1199,11(8), c = 1773,65(11) pm. 2 a crystallizes in the monoclinic space group P2₁/n (No. 14) with a = 875,97(5), b = 1625,36(11), c = 2117,86(12) pm, β = 91,714(7)°. 2 b crystallizes in the triclinic space group P 1 (No. 2) with a = 812,00(10), b = 843,40(10), c = 1179,3(2) pm, α = 100,92(2)°, β = 102,31(2)°, γ = 102,25(2)°.