[cis‐{η2‐(Ph3PAu)2}Ph3PCr(CO)4]·THF,featuring the shortest known separation between two Au metal centres in a heteronuclear Au2M cluster

The title compound, tetra­carbonyl‐1κ⁴C‐tris­(tri­phenyl­phos­phino)‐1κP,2κP,3κP‐triangulo‐chromiumdigold(Au—Au)(2 Cr—Au) tetra­hydro­furan solvate, [Au₂Cr(C₁₈H₁₅P)₃(CO)₄]·C₄H₈O, is a stable isolobal analogue of the extremely labile [(η²‐H₂)CrL_n–1] molecular hydrogen complex (n = 6; L is a neutral ligand, e.g. CO or PPh₃), and features the shortest known separation [2.6937 (2) Å] between two Au atoms in a triangular heteronuclear metal‐cluster framework.     

Formation and structure of diruthenium complexes Ru2(CO)6−n (PPh3) n {μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} (n=1, 2)

Ruthenium carbonyl triphenylphosphine complexes Ru₂(CO)_6−n (PPh₃) _n {μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} (n=1, 2) were obtained by the reaction of complex Ru₂(CO)₆{μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} containing the ruthenacyclopentadiene moiety with PPh₃ in refluxing toluene. The complexes were characterized by IR and by¹H,¹³C, and³¹P NMR spectroscopy, and by X-ray analysis. The monophosphine derivative is identical to the complex formed by fragmentation of the Ru₃(CO)₈(PPh₃){μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} cluster and contains the PPh₃ ligand at the ruthenium atom of the ruthenacyclopentadiene moiety. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1836–1843, September, 1998     

Synthese und Kristallstrukturen von [Cu4(As4Ph4)2(PRR′2)4], [Cu14(AsPh)6(SCN)2(PEt2Ph)8], [Cu14(AsPh)6Cl2(PRR′2)8], [Cu12(AsPh)6(PPh3)6], [Cu10(AsPh)4Cl2(PMe3)8], [Cu12(AsSiMe3)6(PRR′2)6] und [Cu8(AsSiMe3)4(PtBu3)4] (R,R′ = organische Gruppen)

Syntheses and Crystal Structures of [Cu₄(As₄Ph₄)₂(PRR′₂)₄], [Cu₁₄(AsPh)₆(SCN)₂(PEt₂Ph)₈], [Cu₁₄(AsPh)₆Cl₂(PRR′₂)₈], [Cu₁₂(AsPh)₆(PPh₃)₆], [Cu₁₀(AsPh)₄Cl₂(PMe₃)₈], [Cu₁₂(AsSiMe₃)₆(PRR′₂)₆], and [Cu₈(AsSiMe₃)₄(P^tBu₃)₄] (R, R′ = Organic Groups) Through the reaction of CuSCN with AsPh(SiMe₃)₂ in the presence of tertiary phosphines the compounds [Cu₄(As₄Ph₄)₂(PRR′₂)₄] ( 1 – 3 ) ( 1 : R = R′ = ⁿPr, 2 : R = R′ = Et; 3 : R = Me, R′ = ⁿPr) and [Cu₁₄(AsPh)₆(SCN)₂(PEt₂Ph)₈] ( 4 ) can be synthesised. Using CuCl instead of CuSCN results to the cluster complexes [Cu₁₄(AsPh)₆Cl₂(PRR′₂)₈] ( 5–6 ) ( 5 : R = R′ = Et; 6 : R = Me, R′ = ⁿPr), [Cu₁₂(AsPh)₆(PPh₃)₆] ( 7 ) and [Cu₁₀(AsPh)₄Cl₂(PMe₃)₈] ( 8 ). Through reactions of CuOAc with As(SiMe₃)₃ in the presence of tertiary phosphines the compounds [Cu₁₂(AsSiMe₃)₆(PRR′₂)₆] ( 9 – 11 ) ( 9 : R = R′ = Et; 10 : R = Ph, R′ = Et; 11 : R = Et, R′ = Ph) and [Cu₈(AsSiMe₃)₄(P^tBu₃)₄] ( 12 ) can be obtained. In each case the products were characterised by single‐crystal‐X‐ray‐structure‐analyses. As the main structure element 1 – 3 each have two As₄Ph₄^2–‐chains as ligands. In contrast 4 – 12 contain discrete AsR^2–ligands.     

Synthese und Strukturen neuer selenido‐ und selenolatoverbrückter Kupfercluster: [Cu38Se13(SePh)12(dppb)6] (1), [Cu(dppp)2][Cu25Se4(SePh)18(dppp)2] (2), [Cu36Se5(SePh)26(dppa)4] (3), [Cu58Se16(SePh)24(dppa)6] (4) und [Cu3(SeMes)3(dppm)] (5)

Syntheses and Crystal Structures of new Selenido‐ and Selenolato‐bridged Copper Clusters: [Cu₃₈Se₁₃(SePh)₁₂(dppb)₆] (1), [Cu(dppp)₂][Cu₂₅Se₄(SePh)₁₈(dppp)₂] (2), [Cu₃₆Se₅(SePh)₂₆(dppa)₄] (3), [Cu₅₈Se₁₆(SePh)₂₄(dppa)₆] (4), and [Cu₃(SeMes)₃(dppm)] (5) The reactions of copper(I) chloride or copper(I) acetate with monodentate phosphine ligands (PR₃; R = organic group) and Se(SiMe₃)₂ have already lead to the formation of CuSe clusters with up to 146 copper and 73 selenium atoms. If the starting materials and the bidentate phosphine ligands (Ph₂P–(CH₂)_n–PPh₂, n = 1: dppm, n = 3: dppp, n = 4: dppb; Ph₂P–C≡C–PPh₂: dppa) and silylated chalcogen derivates are changed (RSeSiMe₃; R = Ph, Mes) a series of new CuSe clusters can be synthesized. From single crystal X‐ray structure analysis one can characterise [Cu₃₈Se₁₃(SePh)₁₂(dppb)₆] ( 1 ), [Cu(dppp)₂] · [Cu₂₅Se₄(SePh)₁₈(dppp)₂] ( 2 ), [Cu₃₆Se₅(SePh)₂₆(dppa)₄] ( 3 ), [Cu₅₈Se₁₆(SePh)₂₄(dppa)₆] ( 4 ) and [Cu₃(SeMes)₃(dppm)] ( 5 ). In this new class of CuSe clusters, compounds 1 and 4 possess a spherical cluster skeleton, wheras 2 and 3 have a layered cluster core.     

Synthesis and conformational studies of palladium(II) complexes containing [PhP(O)NP(E)Ph]− (E=S or Se)

The ligands [Ph₂P(O)NP(E)Ph₂]⁻ (E=S I; E=Se II) can readily be complexed to a range of palladium(II) starting materials affording new six-membered Pd–O–P–N–P–E palladacycles. Hence ligand substitution reaction of the chloride complexes [PdCl₂(bipy)] (bipy=2,2′-bipyridine), [{Pd(μ-Cl)(L–L)}₂] (HL–L=C₉H₁₃N or C₁₂H₁₃N), [{Pd(μ-Cl)Cl(PMe₂Ph)}₂] or [PdCl₂(PR₃)₂] [PR₃=PPh₃; 2PR₃=Ph₂PCH₂CH₂PPh₂or cis-Ph₂PCH=CHPPh₂] with either I (or II) in thf or CH₃OH gave [Pd{Ph₂P(O)NP(E)Ph₂-O,E}(bipy)]PF₆, [Pd{Ph₂P(O)NP(E)Ph₂-O,E}(L–L)], [Pd{Ph₂P(O)NP(E)Ph₂-O,E}Cl(PMe₂Ph)] or [Pd{Ph₂P(O)NP(E)Ph₂-O,E} (PR₃)₂]PF₆ in good yields. All compounds described have been characterised by a combination of multinuclear NMR [31 P{1 H} and 1 H] and IR spectroscopy and microanalysis. The molecular structures of five complexes containing the selenium ligand II have been determined by single-crystal X-ray crystallography. Three different ring conformations were observed, a pseudo-butterfly, hinge and in the case of all three PR₃ complexes, pseudo-boat conformations. Within the Pd–O–P–N–P–Se rings there is evidence for π-electron delocalisation.     

Synthesis of bridged and linked ruthenium and osmium carbonyl clusters containing a [Au2(Ph2PCH2CH2PPh2)]2+ unit. The crystal and molecular structures of Ru5C(CO)14Au2(Ph2PCH2CH2PPh2) and {Os4H3(CO)12}2Au2(Ph2PCH2CH2PPh2)

Treatment of Au₂(Ph₂PCH₂CH₂PPh₂)Cl₂ with one equivalent of the [Ru₅C(CO)₁₄]²⁻ dianion in the presence of TlPF₆ gives Ru₅C(CO)₁₄Au₂(Ph₂PCH₂CH₂PPh₂) (1) in good yield and the [{Ru₅C(CO)₁₄}₂Au₂(Ph₂PCH₂CH₂PPh₂)]²⁻ (2) anion in low yield. Complex 2 becomes the major product if 2 equivalents of [Ru₅C(CO)₁₄]²⁻ are used. Reaction of [Au₂(Ph₂PCH₂CH₂PPh₂)Cl₂] with 3 equivalents of [H₃Os₄(CO)₁₂]⁻ anion in the presence of TlPF₆ affords {H₃Os₄(CO)₁₂}₂Au₂(Ph₂PCH₂CH₂PPh₂) (3) in reasonable yield. X-ray diffraction studies of 1 and 3 show that they contain the [Au₂(Ph₂PCH₂CH₂PPh₂)]²⁺ fragment in different coordination modes.     

Spectroscopic Study of the Interaction of the Pd(acac)(C3-acac)PPh3Complex with BF3OEt2 in the Presence of PPh3

The interaction between the components of a catalytic system Pd(acac)(C³-acac)PPh₃+nPPh₃+ mBF₃OEt₂(where n= 1–4, m= 0.25–4, and acac is the acetylacetonate ligand) in benzene is examined by UV and IR spectroscopy. With a relative excess of PPh₃(n> m), acacH and [Pd(acac)(PPh₃)₂]⁺BF^– ₄were the main products, whereas BF₂acac and a polynuclear complex of PdF₂with PPh₃also containing Pd²⁺(BF^– ₄)₂units were formed with a relative excess of BF₃OEt₂(n< m).     

Synthesis and structural characterisation of [Au2Pt2(PPh3)4(CN-xylyl)4](PF6)2: A platinum—gold cluster with a flattened butterfly geometry

[Au₂Pt₂(PPh₃)₄(CN-xylyl)₄](PF₆)₂ (CN-xylyl = 2,6-dimethylphenylisocyanide) has been synthesised from [Pt(C₂H₄)(PPh₃)₂] and [Au(CN-xylyl)₂]⁺ in CH₂Cl₂ and in the presence of an excess of CN-xylyl. A single crystal X-ray diffraction study has demonstrated that the metal atoms define a flattened butterfly with the gold atoms occupying the higher connectivity sites and forming a short bond of length 2.590(2) Å. The platinum—gold distances lie in the range 2.710(2)–3.026(2) Å.     

Azidocuprate(II). Die Kristallstruktur von (PPh4)2[Cu2(N3)6]

Azidocuprates(II). Crystal Structure of (PPh₄)₂[Cu₂(N₃)₆] (PPh₄)₂[Cu(N₃)₄] and (PPh₄)₂[Cu₂(N₃)₆], which is already known, are prepared from the corresponding chloro cuprates and excess silver azide in dichloro methane suspension. The azido cuprates form nonexplosive brown crystals of low sensitivity to moisture and are characterized by i.r. spectroscopy. (PPh₄)₂[Cu₂(N₃)₆] was submitted to a X-ray crystallographic structural analysis (4284 observed, independent reflexions, R = 0.034). The compound crystallizes triclinic in the space group P1 with one formula unit per unit cell. The lattice parameters are a = 1047.4 pm; b = 1131.1 pm; c = 1179.4 pm; α = 101.26°; β = 109.31°; γ = 103.42°. The compound consists of PPh₄^⊕ cations and centrosymmetric anions [Cu₂(N₃)₆]^2?, which meet D_2h-symmetry fairly well. In the anions the copper atoms are linked to a planar Cu₂N₂ four-membered ring by the N α atoms of two azide groups. The other azido ligands are bonded terminally and complete coordination number 4 at the Cu atoms which show planar geometry.     

Synthese,Kristallstruktur und spektroskopische Charakterisierung von [Au12(PPh)2(P2Ph2)2(dppm)4Cl2]Cl2

Synthesis, Crystal Structure and Spectroscopic Characterization of [Au₁₂(PPh)₂(P₂Ph₂)₂(dppm)₄Cl₂]Cl₂ The reaction of [(AuCl)₂dppm] (dppm = Ph₂PCH₂PPh₂) with P(Ph)(SiMe₃)₂ in CHCl₃ results in the formation of [Au₁₂(PPh)₂(P₂Ph₂)₂(dppm)₄Cl₂]Cl₂ ( 1 ), the crystal structure of which was determined by single crystal X‐ray analysis (space group P2₁/c, a = 1425.3(3) pm, b = 2803.7(6) pm, c = 2255.0(5) pm, β = 95.00(3)°, V = 8977(3)·10⁶ pm³, Z = 2). The dication in 1 consists of two Au₆P₃ units built by highly distorted Au₃P and Au₂P₂ heterotetrahedra, connected via four bidentate phosphine ligands. Additionally, the compound was characterized by IR‐, UV‐ and NMR spectroscopy. The ³¹P{¹H} NMR spectrum is discussed in detail.     

Site Preference in Multimetallic Nanoclusters: Incorporation of Alkali Metal Ions or Copper Atoms into the Alkynyl‐Protected Body‐Centered Cubic Cluster [Au7Ag8(C≡CtBu)12]+

The synthesis, structure, substitution chemistry, and optical properties of the gold‐centered cubic monocationic cluster [Au@Ag₈@Au₆(C≡C^tBu)₁₂]⁺ are reported. The metal framework of this cluster can be described as a fragment of a body‐centered cubic (bcc) lattice with the silver and gold atoms occupying the vertices and the body center of the cube, respectively. The incorporation of alkali metal atoms gave rise to [M_nAg_8?nAu₇(C≡C^tBu)₁₂]⁺ clusters (n=1 for M=Na, K, Rb, Cs and n=2 for M=K, Rb), with the alkali metal ion(s) presumably occupying the vertex site(s), whereas the incorporation of copper atoms produced [Cu_nAg₈Au_7?n(C≡C^tBu)₁₂]⁺ clusters (n=1–6), with the Cu atom(s) presumably occupying the capping site(s). The parent cluster exhibited strong emission in the near‐IR region (λ_max=818 nm) with a quantum yield of 2 % upon excitation at λ=482 nm. Its photoluminescence was quenched upon substitution with a Na⁺ ion. DFT calculations confirmed the superatom characteristics of the title compound and the sodium‐substituted derivatives.     

Transition metal chemistry of phosphorus based ligands. Ruthenium(II) chemistry of bis(phosphino)amines, X2PN(R)PX2 (R=H or Ph, X=Ph; R=Ph, X2=O2C6H4)

Reactions of CpRuCl(PPh₃)₂ with bis(phosphino)amines, X₂PN(R)PX₂ (1 R=H, X=Ph; 2 R=X=Ph; 3 R=Ph, X₂=O₂C₆H₄) give neutral or cationic mononuclear complexes depending on the reaction conditions. Reaction of 1 with CpRuCl(PPh₃)₂ gives one neutral complex, [CpRu(Cl)(η²-Ph₂PN(H)PPh₂)] (4) and two cationic complexes, [CpRu(η²-Ph₂PN(H)PPh₂)(η¹-Ph₂PN(H)PPh₂)]Cl (5) and [CpRu(PPh₃)(η²-Ph₂PN(H)PPh₂)]Cl (6), whereas the reaction of 2 with CpRuCl(PPh₃)₂ leads only to the isolation of cationic complex, [CpRu(PPh₃)(η²-Ph₂PN(Ph)PPh₂)]Cl (7). The catechol derivative 3, in a similar reaction, affords an interesting mononuclear complex [CpRu(PPh₃){η¹-(C₆H₄O₂)PN(Ph)P(O₂H₄C₆)}₂]Cl (8) containing two monodentate bis(phosphino)amine ligands. The structural elucidation of the complexes was carried out by elemental analyses, IR and NMR spectroscopic data.     

Cluster Build-up Reactions using Di-gold Cationic Fragments: Synthesis and Structural Characterization of [Os7(CO)19(Au2dppm)]

The reaction of the di-gold cation [Au₂(dppx)]²⁺ with the heptanuclear cluster dianion [Os₇(CO)₂₀]^2– affords the mixed metal cluster [Os₇(CO)₂₀{Au₂(dppx)}] (x=m (1), e (2), b (3)). On standing, in solution, this complex undergoes decarbonylation to give the cluster [Os₇(CO)₁₉{Au₂(dppx)}] (x=m (4), e (5), b (6)). The complexes have been characterised spectroscopically, and an X-ray structure determination of the dppm derivative shows that it contains a metal core based on an Os₇ edge-bridged bicapped tetrahedron with the two ₃-Au atoms capping adjacent triangular Os₃ faces of the central tetrahedron. In an analogous reaction, the carbido anion [Os₇(H)C(CO)₁₉]^– affords the neutral cluster [Os₇C(CO)₁₉{Au₂(dppm)}] (7) when treated with [Au₂(dppm)]²⁺ in the presence of base.     

Neue arsinidenverbrückte Mehrkern-Clusterkomplexe des Ag und Au. Die Kristallstrukturen von [Ag14(AsPh)6Cl2(PR3)8], (PR3 = PEt3, PMenPr2, PnPr3), [M4(As4Ph4)2(PR3)4], (M = Ag,PR3 = PEt3, PnPr3; M = Au,PR3 = PnPr3), [Au10(AsPh)4(PhAsSiMe3)2(PnPr3)6]

New Arsinidene-bridged Multinuclear Cluster Complexes of Ag and Au. The Crystal Structures of [Ag₁₄(AsPh)₆Cl₂(PR₃)₈], (PR₃ = PEt₃, PMeⁿPr₂, PⁿPr₃), [M₄(As₄Ph₄)₂(PR₃)₄], (M = Ag, PR₃ = PEt₃, PⁿPr₃; M = Au, PR₃ = PⁿPr₃), [Au₁₀(AsPh)₄(PhAsSiMe₃)₂(PⁿPr₃)₆] The reaction of AgCl with PhAs(SiMe₃)₂ in presence of tertiary phosphines (PR₃) leads to arsinidene-bridged silver clusters with the composition [Ag₁₄(AsPh)₆Cl₂(PR₃)₈], (PR₃ = PEt₃ 1 , PMeⁿPr₂ 2 , PⁿPr₃ 3 ). Further it is possible to obtain the multinuclear complexes [Ag₄(As₄Ph₄)₂(PR₃)₄], (PR₃ = PEt₃ 4 , PMeⁿPr₂ 5 ). In analogy to that [PMe₃AuCl] reacts with PhAs(SiMe₃)₂ and PⁿPr₃ to form the compound [Au₄(As₄Ph₄)₂(PⁿPr₃)₄] 6 , which is isostructurell to 4 and 5 . The gold cluster [Au₁₀(AsPh)₄(PhAsSiMe₃)₂(PⁿPr₃)₆] 7 was obtained from the same solution. The structures were characterized by X-ray single crystal structure analysis. (Crystallographic data see “Inhaltsübersicht”)     

Platinum,iridium and rhodium complexes with substituted bis-(diphenylphosphino)methane ligands Ph2PCH(R)PPh2 (R = Me,Ph or SiMe3)

Substituted phosphines of the type Ph₂PCH(R)PPh₂ and their Pt^II complexes [PtX₂{Ph₂PCH(R)PPh₂}] (R = Me, Ph or SiMe₃; X = halide) were prepared. Treatment of [PtCl₂(NCBu^t)₂] with Ph₂PCH(SiMe₃)-PPh₂ gave [PtCl₂(Ph₂PCH₂PPh₂)], while treatment with Ph₂PCH(Ph)PPh₂ gave [Pt{Ph₂PCH(Ph)PPh₂}₂]Cl₂. Reaction of p-MeC₆H₄C≡CLi or PhC≡CLi with [PtX₂{Ph₂PCH(Me)PPh₂}] gave [Pt(C≡CC₆H₄Me-p)₂-{Ph₂PCH(Me)PPh₂}] (X = I) and [Pt{Ph₂PC(Me)PPh₂}₂](X = Cl),while reaction of p-MeC₆H₄C≡CLi with [Pt{Ph₂PCH(Ph)PPh₂}₂]Cl₂ gave [Pt{Ph₂PC(Ph)PPh₂}₂]. The platinum complexes [PtMe₂(dpmMe)] or [Pt(CH₂)₄(dpmMe)] fail to undergo ring-opening on treatment with one equivalent of dpmMe [dpmMe = Ph₂PCH(Me)PPh₂]. Treatment of [Ir(CO)Cl(PPh₃)₂] with two equivalents of dpmMe gave [Ir(CO)(dpmMe)₂]Cl. The PF₆ salt was also prepared. Treatment of [Ir(CO)(dpmMe)₂]Cl with [Cu(C≡CPh)₂], [AgCl(PPh₃)] or [AuCl(PPh₃)] failed to give heterobimetallic complexes. Attempts to prepare the dinuclear rhodium complex [Rh₂(CO)₃(μ-Cl)(dpmMe)₂]BPh₄ using a procedure similar to that employed for an analogous dpm (dpm = Ph₂PCH₂PPh₂) complex were unsuccessful. Instead, the mononuclear complex [Rh(CO)(dpmMe)₂]BPh₄ was obtained. The corresponding chloride and PF₆ salts were also prepared. Attempts to prepare [Rh(CO)(dpmMe)₂]Cl in CHCl₃ gave [RhHCl(dpmMe)₂]Cl. Recrystallization of [Rh(CO)(dpmMe)₂]BPh₄ from CHCl₃/EtOH gave [RhO₂(dpmMe)₂]BPh₄. Treatment of [Rh(CO)₂Cl₂]₂ with one equivalent of dpmMe per Rh atom gave two compounds, [Rh(CO)(dpmMe)₂]Cl and a dinuclear complex that undergoes exchange at room temperature between two formulae: [Rh₂(CO)₂(μ-Cl)(μ-CO)(dpmMe)₂]Cl and [Rh₂(CO)₂-(μ-Cl)(dpmMe)₂]Cl. This revised version was published online in June 2006 with corrections to the Cover Date.     

Aggregation of Dinuclear Cations [{Au(PR3)}2(μ‐OH)]+ into Dimers Induced by Polyoxometalate (POM) Template Effects

Intercluster compounds, [{(Au{P(p‐XPh)₃})₂(μ‐OH)}₂][α‐SiMo₁₂O₄₀(Au{P(p‐XPh)₃})₂] · nEtOH [X = F ( 1 ), Cl ( 2 )] were synthesized by polyoxometalate (POM)‐mediated clusterization, and were unequivocally characterized by X‐ray crystallography, elemental analysis, thermogravimetric and differential thermal analysis (TG/DTA), Fourier transform infrared (FT‐IR), solid‐state cross‐polarization magic‐angle‐spinning (CPMAS) ³¹P nuclear magnetic resonance (NMR), and solution (¹H, ³¹P{¹H}) NMR spectroscopy. The “dimer‐of‐dinuclear phosphanegold(I) cation”, i.e., [{(Au{P(p‐XPh)₃})₂(μ‐OH)}₂]²⁺ was formed by the self‐assembly of dinuclear phosphanegold(I) cations, i.e., [(Au{P(p‐XPh)₃})₂(μ‐OH)]⁺, through inter‐cationic aurophilic interactions as the crossed‐edge arrangement (or tetrahedral Au₄ structure) for 1 , while as the parallel‐edge arrangement (or rectangular Au₄ structure) for 2 . The latter arrangement was first attained only by assistance of the POM. The POM anions in 1 and 2 contained two mononuclear phosphanegold(I) cations, i.e., [Au{P(p‐XPh)₃}]⁺, linked to the OMo₂ oxygen atoms of edge‐sharing MoO₆ octahedra. In the solution ³¹P{¹H} NMR of 1 and 2 , we observed single signals due to the rapid exchange of the phosphanegold(I) units. This shows that the OMo₂ oxygen atoms of edge‐sharing MoO₆ octahedra in the Keggin POM act as multi‐centered active binding sites for the formation of [{(Au{P(p‐XPh)₃})₂(μ‐OH)}₂]²⁺.     

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”.     

Neue amido‐ und imidoverbrückte Kupferkomplexe – Synthesen und Strukturen von [{Li(OEt2)}2][Cu(NPh2)3], [ClCuN(SnMe3)3], [{CuN(SnMe3)2}4], [Cu16(NH2tBu)12Cl16], [{CuNHtBu}8], [Li(dme)3][Cu6(NHMes)3(NMes)2], [PPh3(C6H4)CuNHMes], [{[Li(dme)][Cu(NHMes)(NHPh)]}2] und [{Li(dme)3}3][Li(dme)2][Cu12(NPh)8]

New Amido and Imido Bridged Complexes of Copper – Syntheses and Structures of [{Li(OEt₂)}₂][Cu(NPh₂)₃], [ClCuN(SnMe₃)₃], [{CuN(SnMe₃)₂}₄], [Cu₁₆(NH₂^tBu)₁₂Cl₁₆], [{CuNH^tBu}₈], [Li(dme)₃][Cu₆(NHMes)₃(NMes)₂], [PPh₃(C₆H₄)CuNHMes], [{[Li(dme)][Cu(NHMes)(NHPh)]}₂], and [{Li(dme)₃}₃][Li(dme)₂][Cu₁₂(NPh)₈] The reactions of stannylated and lithiated amines with coppersalts (halogenides, thiocyanates) lead to amido and imido bridged complexes which contain one to twelve metal atoms. [{Li(OEt₂)}₂][Cu(NPh₂)₃] ( 1 ) results from the reaction of CuCl with LiNPh₂ in the presence of trimethylphosphine. With N(SnMe₃)₃, CuCl reacts to the donor‐acceptor complex [ClCuN(SnMe₃)₃] ( 2 ) that is transformed into the tetrameric complex [{CuN(SnMe₃)₂}₄] ( 3 ) by thermolysis. 3 can also be obtained by the reaction of LiN(SnMe₃)₂ with Cu(SCN)₂. While terminally bound in 1 , the amido ligand is μ₂‐bridging between copper atoms in compound 3 . The influence of the alkyl amide's leaving group can be seen from a comparison of the reactivity of Me₃SnNH^tBu and LiNH^tBu, respectively. With Me₃SnNH^tBu, CuCl₂ forms the polymeric compound [Cu₁₆(NH₂^tBu)₁₂Cl₁₆] ( 4 ) whereas in the case of LiNH^tBu with both CuCl and CuSCN, the complex [{CuNH^tBu}₈] ( 5 ) is obtained. The latter contains two planar Cu₄N₄‐rings similar to those in 3 . If a mesityl group is introduced at the lithium amide, different products are accessible. Both, CuBr and CuSCN, lead to the formation of [Li(dme)₃][Cu₆(NHMes)₃(NMes)₂] ( 6 ) whose anion consists of a prismatic copper core with μ₂‐bridging amido and μ₃‐bridging imido ligands. In the presence of PPh₄Cl, a mixture of Cu(SCN)₂ and LiNHMes enables an ortho‐metallation reaction that produces [PPh₃(C₆H₄)CuNHMes] ( 7 ). From the reaction of CuSCN with LiNHMes and LiNHPh either the dimeric complex [{[Li(dme)][Cu(NHMes)(NHPh)]}₂] ( 8 ) or the cluster [{Li(dme)₃}₃][Li(dme)₂][Cu₁₂(NPh)₈] ( 9 ) results. The anion in 9 exhibits a cubo‐octahedron of copper atoms μ₃‐bridged by (NPh)^2–‐ligands. The solid state structures of compounds 1 – 9 have been determined by single crystal X‐ray diffraction.     

Neue Kupfertellurid‐Cluster – Synthesen,Kristallstrukturen und optische Spektren

New Coppertelluride Clusters – Syntheses, Crystal Structures, and Optical Spectra Reactions of copper(I) acetate with Te(SiMe₃)₂ lead in the presence of tertiary phophines PR₃ (R = organic group) to the formation of new coppertelluride clusters: [Cu₈Te₄(PPh₃)₇] ( 1 ), [Cu₁₆Te₉(PPh₃)₈] ( 2 ), [Cu₂₃Te₁₃(PPh₃)₁₀] ( 3 ), [Cu₄₄Te₂₃(PPh₃)₁₅] ( 4 ), [Cu₁₂Te₆(PPh₃)₈] ( 5 ), [Cu₂₆Te₁₂(PEt₂Ph)₁₂] ( 6 ), [Cu₁₆Te₈(PⁿPr₂Ph)₁₀] ( 7 ), [Cu₄₄Te₂₃(PⁿPr₂Ph)₁₅] ( 8 ), [Cu₂₄Te₁₂(PⁱPr₃)₁₂] ( 9 ). Simple electron counting on the basis of Cu¹⁺ and Te^2– suggests that the smaller and medium size clusters 1 , 5 , 7 , and 9 are electron precise compounds and that on the other hand some of the medium size and larger ones 2 , 3 , 4 , and 8 must contain mixtures of Cu¹⁺/Cu²⁺ ions or 6 Cu¹⁺ ions and Cu⁰ atoms. UV‐VIS spectra in the solid state strongly confirms this suggestion by showing broad intervalence bands in the region of higher wavelengths for the cluster compounds formally being not electron precise. Apparently there is also an interesting dependence of these intervalence bands on the size of the cluster molecules.     

Reactions of [ReOX3(PPh3)2] Complexes (X = Cl,Br) with Phenylacetylene and the Structures of the Products

Oxorhenium(V) complexes [ReOX₃(PPh₃)₂] (X = Cl, Br) react with phenylacetylene under formation of complexes with ylide‐type ligands. Compounds of the compositions [ReOCl₃(PPh₃){C(Ph)C(H)(PPh₃)}] ( 1 ), [ReOBr₃(OPPh₃){C(Ph)C(H)(PPh₃)}] ( 2 ), and [ReOBr₃(OPPh₃){C(H)C(Ph)(PPh₃)}] ( 3 ) were isolated and characterized by X‐ray diffraction. They contain a ligand, which was formed by a nucleophilic attack of released PPh₃ at coordinated phenylacetylene. The structures of the products show that there is no preferable position for this attack. Cleavage of the Re–C bond in 3 and dimerization of the organic ligand resulted in the formation of the [{(PPh₃)(H)CC(Ph)}₂]²⁺ cation, which crystallized as its [(ReOBr₄)(OReO₃)]^2– salt.