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]⁺.     

Photochemical reactions of M(CO)6 (M = Cr,Mo, W) with Ph2P(S)P(S)Ph2

New complexes {M(CO)₄[Ph₂P(S)P(S)Ph₂]} (M = Cr, Mo and W), (1a)–(3a), [(1a), M = Cr; (2a), M = Mo; (3a), M = W] and {M₂(CO)₁₀[-Ph₂P(S)P(S)Ph₂]} (M = Cr, Mo, W), [(1b)–(3b) [(1b), M = Cr; (2b), M = Mo; (3b), M = W]] have been prepared by the photochemical reaction of M(CO)₆ with Ph₂P(S)P(S)Ph₂ and characterized by elemental analyses, f.t.-i.r. and ³¹P-(¹H)-n.m.r. spectroscopy and by FAB-mass spectrometry. The spectra suggest cis-chelate bidentate coordination of the ligand in {M(CO)₄[Ph₂P(S)P(S)Ph₂]} and cis-bridging bidentate coordination of the ligand between two metals in (M = Cr, Mo and W).     

Perfluormethyl-Element-Liganden. XVIII. Darstellung und spektroskopische Untersuchung von M(CO)5L und M(CO)4L2-Komplexen [L = MenP(CF3)3−n; n = 0–3; M = Cr,Mo, W]

Perfluoromethyl-Element-Ligands. XVIII. Preparation and Spectroscopic Investigation of M(CO)₅L and M(CO)₄L₂ Complexes [L = Me_nP(CF₃)_3?n; n = 0–3; M = Cr, Mo, W] M(CO)₅L and cis-M(CO)₄L₂ complexes, respectively [M = Cr, Mo, W; L = Me_nP(CF₃)_3?n; n = 0–3] are prepared reacting M(CO)₅ · THF or M(CO)₄norbor with L at room temperature. The cis-compounds isomerize above 50°C yielding the trans-complexes; the rate of isomerization increases with increasing number of CF₃ groups. Thermal reaction of M(CO)₆ (M = Cr, Mo, W) with P(CF₃)₃ yields M(CO)₅P(CF₃)₃ and trans-M(CO)₄[P(CF₃)₃]₂. Introduction of three P(CF₃)₃ ligands by reaction with M(CO)₃(cycloheptatriene) (M = Cr, Mo) proves unsuccessful; besides little M(CO)₅P(CF₃)₃ trans-M(CO)₄[P(CF₃)₃]₂ is formed. The new compounds are characterized by analytical and spectroscopic (n.m.r., i.r., MS) methods.     

Perfluormethyl-Element-Liganden. XXXII. Reaktionen der Metallhydride π-C5H5(CO)3MH (M = Cr,Mo, W) mit Diphosphanen [Ph2−nYnP]2 (Y = I,CN, SiMe3; n = 2, 1, 0)

Perfluoromethyl Element Ligands. XXXII. Reactions of the Metal Hydrides π-C₅H₅(CO)₃MH (M = Cr, Mo, W) with Diphosphanes [Ph_2?nY_nP]₂ (Y = I, CN, SiMe₃; n = 2, 1, 0) The reactions of π-C₅H₅(CO)₃MH (M = Cr, Mo, W) ( 1a – c ) with the symmetric diphosphanes (Ph₂P)₂, [Ph(CN)P]₂, [(CN)₂P]₂, and the cyclophosphane (PPh)₅, respectively, occur under cleavage of the P? P bond. The reactivity decreases in the series The tendency to form binuclear complexes reflects the basicity of the metallated phosphanes π-C₅H₅(CO)₃MPRR′ and increases in the order P(CN)₂ < P(CN)Ph ? P(Ph)H < PPh₂. Iodine containing diphosphanes [Ph(I)P? P(I)Ph and P₂I₄] undergo redox reactions with 1a – c , yielding π-C₅H₅(CO)₃MI and unstable iodo-diphosphanes. No P? P bond cleavage occurs in the reaction of the silyl substituted diphosphanes [Ph(SiMe₃)P]₂ and [(Me₃Si)₂P]₂ with 1a – c , but P? Si bond fission is the preferred reaction giving π-C₅H₅(CO)₃MSiMe₃.     

Metallkomplexe von Phenylenbistriazeniden: Synthese und Kristallstrukturen von [Cp(CO)2M]2(1,2-PhN3C6H4N3Ph) (M = Mo,W)

Metal Complexes of Phenylenebistriazenides: Synthesis and Crystal Structures of [Cp(CO)₂M]₂(1,2-PhN₃C₆H₄N₃Ph) (M = Mo, W) [Cp(CO)₂M]₂(1,2-PhN₃C₆H₄N₃Ph) [(M = Mo( 1 ), M = W( 2 )] is formed in the reaction of Cp(CO)₃MCl with PhN₃(H)C₆H₄N₃(H)Ph and C₂H₅ONa in a THF/ethanol mixture. 1 crystallizes from toluene as dark red crystals (triclinic, P1 , a = 1 499.3(9) pm, b = 1 734.0(7) pm, c = 1 852.8(8) pm, α = 66.84(3)°, β = 78.25(4)°, γ = 77.19(4)°). The unit cell contains four complexes with two independent complexes in the asymmetric unit, and eight solvent molecules. 2 crystallizes from THF as yellow crystals free from solvent molecules (triclinic, P1 , a = 979.0(5) pm, b = 1 152.8(5) pm, c = 1 475.8(5) pm, α = 98.26(4)°, β = 104.93(4)°, γ = 101.03(4)°, Z = 2). 1 and 2 are discrete molecular complexes with a 1,2-bis(phenyltriazenido)phenylligand, (PhN₃C₆H₄N₃Ph)^2?, chelating the metal atoms of two Cp(CO)₂M units with the N atoms N1 and N3 of both N₃ groups. Due to the sterical pretension of the Cp(CO)₂M units the phenylenebistriazenido ligand deviates strongly from planarity that is found in the metal complexes characterized so far.     

Phosphido- und arsenido-verbrückte Zweikernkomplexe: Synthese und Struktur von (η5-C5H4R)2Zr{μ-P(SiMe3)2}2M(CO)4 (R = Me,M = Cr; R = H,M = Mo) sowie die Synthese von (η5-C5H5)2Zr{μ-As(SiMe3)2}2Cr(CO)4

Phosphido- and Arsenido-bridged Dinuclear Complexes. Synthesis and Molecular Structure of (η⁵-C₅H₄R)₂Zr{μ-P(SiMe₃)₂}₂M(CO)₄ (R = Me, M = Cr; R = H, M = Mo) and Synthesis of (η⁵-C₅H₅)₂Zr{μ-As(SiMe₃)₂}₂Cr(CO)₄ The reaction of (η⁵-C₅H₄R)₂Zr{E(SiMe₃)₂}₂ with M(CO)₄(NBD) (NBD = norbornadiene) yields the dinuclear phosphido- or arsenido-bridged complexes (η⁵-C₅H₄R)₂Zr{μ-E(SiMe₃)₂}₂M(CO)₄ (R = Me, E = P, M = Cr ( 1 ); R = H, E = P, M = Mo ( 2 ); R = H, E = As, M = Cr ( 3 )). No formation of dinuclear complexes was observed in the reaction of (η⁵-C₅H₄Me)₂Zr{P(SiMe₃)₂}₂ with Ni(PEt₃)₄, Ni(CO)₂(PPh₃)₂ or with NiCl₂(PPh₃)₂ in the presence of Mg. Complexes 1 – 3 were characterised spectroscopically (i. r., n. m. r., m. s.), and X-ray structure investigations were carried out on 1 and 2 . The central four-membered ZrP₂M ring is slightly puckered (dihedral angle between planes ZrP₂/CrP₂ 14.7°, ZrP₂/MoP₂ 14.2°). The Zr? P bond lengths are equivalent ( 1 : Zr? P1 2.654(4), Zr? P2 2.657(4) Å; 2 : Zr? P1 2.6711(9), Zr? P2 2.6585(7) Å), as are the M? P bond lengths (M = Cr ( 1 ): Cr? P1 2.513(4), Cr? P2 2.502(4) Å; M = Mo ( 2 ): Mo? P1 2.6263(7), Mo? P2 2.6311(10) Å). The long Zr ··· M distances of 3.414 Å (M = Cr ( 1 )) and 3.461 Å (M = Mo ( 2 )) indicate the absence of a metal-metal bond.     

Novel Transition‐Metal (M=Cr,Mo, W,Fe) Carbonyl Complexes with Bis(guanidinato)silicon(II) Ligands

The donor‐stabilized silylene 2 (the first bis(guanidinato)silicon(II ) complex) reacts with the transition‐metal carbonyl complexes [M(CO)₆] (M=Cr, Mo, W) to form the respective silylene complexes 7 – 10 . In the reactions with [M(CO)₆] (M=Cr, Mo, W), the bis(guanidinato)silicon(II ) complex 2 behaves totally different compared with the analogous bis(amidinato)silicon(II ) complex 1 , which reacts with [M(CO)₆] as a nucleophile to replace only one of the six carbonyl groups. In contrast, the reaction of 2 leads to the novel spirocyclic compounds 7 – 9 that contain a four‐membered SiN₂C ring and a five‐membered MSiN₂C ring with a M?Si and M?N bond (nucleophilic substitution of two carbonyl groups). Compounds 7 – 10 were characterized by elemental analyses (C, H, N), crystal structure analyses, and NMR spectroscopic studies in the solid state and in solution.     

Synthesis and Spectra of Cationic Bis(tertiary phosphine) derivatives of cycloheptatrienyliummolybdenum and cyclopentadienyliron complexes

Reaction of [(η-C₇H₇)Mo(CO)₃][PF₆] and [(η-C₅H₅)Fe(CO)₂CH₃CN][PF₆] with ditertiary phosphine ligands afforded products of three types; the monosubstituted complexes [(Ring)M(CO)₂Ph₂P(CH₂)_nPPh₂][PF₆] (Ring = η-C₇H₇, M = Mo, N = 1; Ring = η-C₅H₅, M = Fe, N = 1 and 2), the chelated complexes [(Ring)M(CO)Ph₂P(CH₂)_nPPh₂][PF₆] (Ring = η-C₇H₇, M = Mo, N = 1 and 2; Ring = η-C₅H₅, M = Fe, N = 1 and 2), and the dinuclear complex [{(η-C₇H₇)Mo(CO)₂}₂ -μ- Ph₂PCH₂CH₂PPh₂][(PF₆)₂]. Spectroscopic properties, including ³¹P NMR, are reported.     

IV Dodekaedrische [Mo(CN)8]‐Koordination in den cyanoverbrückten Cobalt‐ und Nickel‐Amminkomplexen MII2(NH3)8[Mo(CN)8] · 1,5 H2O (MII = Co,Ni) und Ni2(NH3)9[Mo(CN)8] · 2 H2O

Crystal Structures of Octacyanomolybdates(IV). IV Dodecahedral [Mo(CN)₈] Coordination of the Cyano‐Bridged Cobalt and Nickel Ammin Complexes M^II₂(NH₃)₈[Mo(CN)₈] · 1.5 H₂O (M^II = Co, Ni) and Ni₂(NH₃)₉[Mo(CN)₈] · 2 H₂O At single crystals of the hydrated cyano complexes Co₂(NH₃)₈[Mo(CN)₈] · 1.5 H₂O (a = 910.0(4), b = 1671(2), c = 1501(1) pm, β = 93.76(6)°) and Ni₂(NH₃)₈[Mo(CN)₈] · 1.5 H₂O (a = 899.9(9), b = 1654.7(4), c = 1488(1) pm, β = 94.01°), isostructurally crystallizing in space group P2₁/c, Z = 4, and of trigonal Ni₂(NH₃)₉[Mo(CN)₈] · 2 H₂O (a = 955.1(1), c = 2326.7(7) pm, P3₁, Z = 3), X‐ray structure determinations were performed at 168 resp. 153 K. The [Mo(CN)₈]^4– groups of the three compounds, prepared at about 275 K and easily decomposing, show but slightly distorted dodecahedral coordination (mean distances Mo–C: 216.3, 215.4 and 216.1 pm). Within the monoclinic complexes the anions twodimensionally form cyano bridges to the ammin cations [M(NH₃)₄]²⁺ and are connected with the resulting [MN₆] octahedra (Co–N: 215.1 pm, Ni–N: 209.8 pm) into strongly puckered layers. The trigonal complex exhibits a chain structure, as one [Ni(NH₃)₅]²⁺ cation is only bound as terminal octahedron (Ni–N: 212.0 pm). Details and the influence of hydrogen bridges are discussed.     

Synthese und Kristallstruktur von (C5H5)Mo(CO)3(AuPPh3) und [(C5H5)Mo(CO)2(AuPPh3)4]PF6

Synthesis and Crystal Structure of (C₅H₅)Mo(CO)₃(AuPPh₃) and [(C₅H₅)Mo(CO)₂(AuPPh₃)₄]PF₆ CpMo(CO)₃(AuPPh₃) is obtained by the reaction of Li[CpMo(CO)₃] with Ph₃PAuCl at ?95°C in CH₂Cl₂. It crystallizes in the monoclinic space group C2/c with a = 2625.1(7), b = 883.2(1), c = 2328.4(7) pm, β = 116.39(1)° und Z = 8. In the complex the AuPPh₃ group is coordinated to the CpMo(CO)₃ fragment with a Au? Mo bond of 271,0 pm. The Mo atom thus achieves a square pyramidal coordination with the center of the Cp ring in apical position. CpMo(CO)₃(AuPPh₃) reacts under uv irradiation with an excess of Ph₃PAuN₃ to afford the cluster cation [CpMo(CO)₂(AuPPh₃)₄]⁺. It crystallizes as [CpMo(CO)₂(AuPPh₃)₄]PF₆ · 2 CH₂Cl₂ in the orthorhombic space group P2₁2₁2₁ with a = 1553.9(1), b = 1793.8(2), c = 2809.8(7) pm und Z = 4. The five metal atoms form a trigonal bipyramidal cluster skeleton with the Mo atom in equatorial position. The Mo? Au distances range from 275.5 to 280.8 pm, and the Au? Au distances are between 281.2 and 285.6 pm.     

Addition des O'Donnell Reagenzes [Ph2C=NCHCO2Me]– an π-koordinierte,ungesättigte Kohlenwasserstoffe in [(C6H7)Fe(CO)3]+, [(C7H9)Fe(CO)3]+, [(C7H7)M(CO)3]+ (M = Cr,Mo) und [(C2H4)Re(CO)5]+. α-Aminosäuren mit metallorganischen Seitenketten

Metal Complexes of Biologically Important Ligands. CXVII [1] Addition of the O'Donnell Reagent [Ph₂C=NCHCO₂Me]^– to Coordinated, Unsaturated Hydrocarbons of [(C₆H₇)Fe(CO)₃]⁺, [C₇H₉Fe(CO)₃]⁺, [(C₇H₇)M(CO)₃]⁺ (M = Cr, Mo), and [(C₂H₄)Re(CO)₅]⁺. α-Amino Acids with Organometallic Side Chains The addition of [Ph₂C=NCHCO₂Me]^– to [(C₆H₇)Fe(CO)₃]⁺, [(C₇H₉)Fe(CO)₃]⁺, [(C₇H₇)M(CO)₃]⁺ (M = Cr, Mo) and [(C₂H₄)Re(CO)₅]⁺ gives derivatives of α-amino acids with organometallic side chains. The structure of [(η⁴-C₆H₇)CH(N=CPh₂)CO₂Me]Fe(CO)₃ was determined by X-ray diffraction. From the adduct of [Ph₂C=NCHCO₂Me]^– and [(C₇H₇)Mo(CO)₃]⁺ the Schiff base of a new unnatural α-amino acid, Ph₂C=NCH(C₇H₇)CO₂Me, was obtained.     

Synthesis of the New Silanediyldiphosphinite tBu2Si(OPPh2)2 and its Reactions with the Norbornadiene Complexes C7H8M(CO)4 (M = Cr,Mo, W). Crystal Structures of cis-M(CO)4[tBu2Si(OPPh2)2] (M = Cr,Mo)

Silanediyldiphosphinite tBu₂Si(OPPh₂)₂ 1 has been synthesised. 1 reacts with the norbornadiene complexes C₇H₈M(CO)₄ (M = Cr, Mo, W) to give six-membered chelate rings of the type cis-M(CO)₄[tBu₂Si(OPPh₂)₂] 2–4 . The crystal structures of the chromium and molybdenum complexes cis-Cr(CO)₄[tBu₂Si(OPPh₂)₂] 2 and cis-Mo(CO)₄[tBu₂Si(OPPh₂)₂] 3 have been determined. Both complexes crystallise in the triclinic system (space group P1 ) with unit cell parameters: ( 2 ) a = 1 093(3) pm, b = 1 477(5) pm and c = 1 542(5) pm; α = 108.4(2)°, b? = 103.87(11)° and b? = 104.57(10)°; U = 2.143(12) nm³; Z = 2; ( 3 ) a = 1 097.8(2) pm, b = 1 483.7(2) pm and c = 1 554.3(2) pm; α = 108.10(1)°, b? = 103.956(6)° and γ = 104.213(7)°; U = 2.1899(6) nm³; Z = 2. Both 2 and 3 consist of discrete, slightly distorted, octahedral monomers in which the six-membered chelate rings are essentially planar. In contrast, the conformations of the chelate rings found in crystal structures of analogous complexes vary from twist-boat to “chaise longue”.     

Synthese von Nitrenkomplexen mit N-Trimethylsilylanilin. II. Charakterisierung und Kristallstruktur der Rhenium(V)-phenylnitren-Komplexe mer-[Re(NPh)Cl3(NH2Ph)(Ph3P)] und trans-[Re(NPh)(OMe)Cl2(Ph3P)2]

Synthesis of Phenylnitrene Complexes with N-Trimethylsilylaniline. II. Characterization and Crystal Structure of the Rhenium(V) Complexes mer-[Re(NPh)Cl₃(NH₂Ph)(Ph₃P)] and trans-[Re(NPh)(OMe)Cl₂(Ph₃P)₂] Reaction of [ReOCl₃(Ph₃P)₂] with N-trimethylsilylaniline yields mer-[Re(NPh)Cl₃(Ph₃P)₂], which reacts under air with excess of N-trimethylsilylaniline to form [Re(NPh)Cl₃ · (NH₂Ph)(Ph₃P)]. Crystallization from CH₂Cl₂/MeOH affords [Re(NPh)(OMe)Cl₂(Ph₃P)₂] as an additional product. [Re(NPh)Cl₃(NH₂Ph)(Ph₃P)] crystallizes in the monoclinic space group P2₁/n with a = 1 192.3(3); b = 1 918.9(3); c = 1 266.3(3) pm; β = 101.71(1)°; Z = 4. The rhenium atom has a distorted octahedral environment with the Cl atoms in meridional positions. The phenyl nitrene ligand is coordinated with an almost linear arrangement Re? N1? C40 = 166.8(6)° and with a bond distance Re?N = 170.5(6) pm. [Re(NPh)(OMe)Cl₂(Ph₃P)₂] · 1/2CH₂Cl₂ crystallizes in the triclinic space group P1 : a = 1 103.1(4); b = 1 227.9(4); c = 1 711.3(5) pm; α = 70.48(3)°; β = 72.71(3)°; γ = 80.03(3)°; Z = 2. The rhenium atom exhibits a distorted octahedral coordination with the Cl atoms and the phosphine ligands in trans positions. As a consequence of the competition of the nitrene ligand and the trans-coordinated methoxy group the Re?;N bond length is slightly lengthened to 173.2(7) pm, while the Re? O bond length of 193.4(6) pm is short. The bond angles Re? N? C70 and Re? O? C80 are 173.3(7)° and 139.1(7)°, respectively.     

Mono- und Di-t-butylcyclopentadienyl-Carbonyl-Komplexe des Eisens und Molybdäns. Die Kristallstruktur von [Cp″Mo(Co)2]2 (Cp″ = n5-C5H3t-Bu2-1,3)

Mono- and Di-t-Butylcyclopentadienyl Carbonyl Complexes of Iron and Molybdenum — Crystal Structure of [Cp″Mo(CO)₂]₂ (Cp″ = n⁵-C₅H₃-t-Bu₂-1,3) Cothermolysis of M(CO)_m (M = Fe, m = 5; M = Mo, m = 6) with t-Bu-substituted cyclopentadienyls constitutes a simple synthesis of complexes of the type [Cp*M(CO)_n]₂ (CP* = n⁵-C₅H₃ (t-Bu), R, R = H, t-Bu; M = Fe, Mo; n = 2, 3). Each synthesis has an optimal temperature. The yield of Fe complexes decreases at temperatures above 130°C because of decomposition of the product. Optimal yields of [Cp*Mo(CO)₃]₂ are obtained at 130–140°C, whereas at 160°C complexes of the type [Cp*Mo(CO)₂]₂ with formal Mo? Mo triple bonds are obtained. The structure of the complexes is discussed on the basis of ¹H-, ¹³C-NMR, IR, and mass spectrometry. The structure of [Cp″Mo(CO)₂]₂ (Cp″ = n⁵-C₅H₃t-Bu₂-1,3) was determined by X-ray crystallography at ?95°C. It crystallises in the space group Pbca, with cell constants a = 1808.6(6), b = 1308.5(4), c = 2507.9(9) pm, Z = 8, R = 0.031 for 3794 reflections. The Mo? Mo bond length of 253.3 pm is very long for a formal triple bond. The Cp″? Mo? Mo? Cp″ axis is non-linear.     

Triorganoantimon- und Triorganobismutdisulfonate Kristall- und Molekülstrukturen von (C6H5)3M(O3SC6H5)2 (M = Sb,Bi)

Triorganoantimony and Triorganobismuth Disulfonates. Crystal and Molecular Structure of (C₆H₅)₃M(O₃SC₆H₅)₂(M = Sb, Bi) Triorganoantimony disulfonates R₃Sb(O₃SR′)₂ [R = CH₃ = Me, C₆H₅ = Ph; R′ = Me, CH₂CH₂OH, Ph, 4-CH₃C₆H₄. R = Ph; R′ = 2,4-(NO₂)₂C₆H₃], Me₃Sb(O₃SCF₃)₂ · 2 H₂O and triphenylbismuth disulfonates Ph₃Bi(O₃SR′)₂ [R = Me, CF₃, CH₂CH₂OH, Ph, 4-CH₃C₆H₄, 2,4-(NO₂)₂C₆H₃] have been prepared by reaction of Me₃Sb(OH)₂, (Ph₃SbO)₂, and Ph₃BiCO₃, respectively, with the appropriate sulfonic acids. From vibrational data an ionic structure is inferred for Me₃Sb(O₃SCF₃)₂ · 2 H₂O and Me₃Sb(O₃SCH₂CH₂OH)₂, and a covalent structure for the other compounds with a penta-coordinated central atom with trigonal bipyramidal surrounding (Ph or Me in equatorial, unidentate sulfonate ligands in apical positions). Ph₃M(O₃SPh)₂ (M = Sb, Bi) crystallize monoclinic [space group P2₁/c; M = Sb/Bi: a = 1 611.5(8)/1 557.4(9), b = 987.5(6)/1 072,5(8), c = 1 859.9(9)/1 696.5(9) pm, β = 105.71(5)/96.62(5)°; Z = 4; d(calc.) 1.556/1.781 Mg · m^?3; V_cell = 2 849.2 · 10⁶/2 814.8 · 10⁶ pm³; structure determination from 3 438/3 078 independent reflexions (I ≥ 3σ(I)), R(unweighted) = 0.030/0.029]. M is bonding to three Ph groups in the equational plane [mean distances Sb/Bi? C:210.1(4)/219.1(7) pm] and two sulfonate ligands with O in apical positions [distances Sb? O: 210.6(3), 212.8(2); Bi? O: 227.6(5), 228.0(4) pm]. Weak interaction of M with a second O atom of one sulfonate ligand is inferred from a rather short M? O contact distance [Sb? O: 327.4(4), Bi? O: 312.9(5) pm], and from the distortion of equatorial angles [C? Sb? C: 128.4(2), 119.2(2), 112.2(2); C? Bi? C: 135.9(3), 117.8(3), 106.3(3)°]     

Synthesis,Characterization, and Electronic Structure of Thiometallato Complexes of Cobalt of the Type [Co(TM)2]m− with Different Electron Populations

Synthetic, spectroscopic (IR, UV/VIS/NIR, EPR), and electrochemical studies have been carried out for complexes of the type [Co(MO_4–nS_n)₂]^2? (M = Mo, W; n = 2, 3, 4) and most of the corresponding trianions [Co(MoO_4–nS_n)₂]^3?, which can be obtained from the dianions by reduction. The complexes have delocalized electronic ground states and remarkable metal-ligand interactions, leading to unusual electronic absorption spectra. The electronic structure and the electrochemical properties of the species existing with different electron populations are also discussed in relation to those of other 3 d transition metal thiometallato complexes. The crystal structures of [(Ph₃P)₂N]₂[Et₄N][Co(MS₄)₂] · 2 CH₃CN (M = W ( 1 ), Mo ( 2 )) have been determined. The compounds crystallize in the orthorhombic space group P2₁2₁2 (Z = 2) with unit cell dimensions: a = 1252.6(4), b = 3385.2(7), c = 1077.6(3) for 1 ; a = 1261.0(9), b = 3393.2(28), c = 1084.4(7) pm for 2 . The structure of the anions consists of two tetrahedral MS₄ units acting as bidentate ligands to the central Co atoms with significant deviation from idealized D_2d symmetry (W? ;Co? ;W = 168.3(2), Mo? ;Co? ;Mo = 169.6(8)°). Averaged interatomic distances (pm) for 1 are as follows (values for 2 in brackets): Co? ;S_br = 224.4 (219), Co? ;M = 272.7 (275), M? ;S_br = 223.0 (223), M? ;S_term = 217.5 (215) pm. Investigations of complex formation in solution, using electronic absorption spectroscopy and cyclic voltammetry, allowed physical data of those species which could not be isolated in crystalline form to be obtained.     

Chemie polyfunktioneller Moleküle. 97. Beiträge zur Komplexchemie des Lithium-bis(diphenylphosphino)amids,des Bis(diphenylphosphino)amins und des Tris(diphenylphosphino)amins

Chemistry of Polyfunctional Molecules. 97. Contributions to the Coordination Chemistry of Lithium-bis(diphenylphosphino)amide, Bis(diphenylphosphino)amine, and Tris(diphenyl-phosphino)amine (Ph₂P)₂NLi ( 1 ) forms with AuCl(PPh₃) the already known complex [Au(Ph₂P)₂N]₂ ( 2 ), which now has been proved by mass spectroscopy to possess the postulated dimeric structure. 2 gives with HCl, HClO₄, and HBF₄ the new compounds [ClAu(Ph₂P)₂NH]₂ ( 3a ) and [Au(Ph₂P)₂NH…?X]₂ [X = ClO₄ ( 3b ), BF₄ ( 3c )]. In analogy the neutral complex Fe(C₅H₅)(CO)(Ph₂P)₂N ( 5 ) os obtained from FeCl(C₅H₅)(CO)₂ and 1. 5 reacts with HCl to [Fe(C₅H₅)(CO)(Ph₂P)₂NH…?Cl] ( 6a ). The last one can also be prepared by direct reaction of FeCl(C₅H₅)(CO)₂ with (Ph₂P)₂NH ( 4 ). In the same way FeBr(C₅H₅)(CO)₂ reacts with 4 yielding [Fe(C₅H₅)(CO)(Ph₂P)₂NH…?Br] ( 6b ), which leads under metathesis with NH₄PF₆ to [Fe(C₅H₅)(CO)(Ph₂P)₂NH]PF₆ ( 6c ). With PdCl₂(NCPh)₂ the ligand 1 forms Pd[(Ph₂P)₂N]₂ ( 7 ), which also can be synthesized in another way, but is now for the first time characterized in a spectroscopically detailed manner. Cr(CO)₄(Ph₂P)₂NPPh₂ reacts with AuCl(CO) to Cr(CO)₄(Ph₂P)₂NPPh₂AuCl ( 8 ). This compound gives with Cr(CO)₄(Ph₂P)₂NLi the trimetallic complex (OC)₄Cr(Ph₂P)₂NPPh₂AuN(PPh₂)₂Cr(CO)₄ ( 9 ). (Ph₂P)₃N ( 10 ) yields with AuCl(CO) in the molar ratio of 1:3 the compound [ClAuPh₂P]₃N ( 11 ).     

Kristallstrukturen von Octacyanomolybdaten(IV). III [1] (NMe4)3Li[Mo(CN)8] · 3,5 H2O und Cs7Na[Mo(CN)8]2 · 4,17 H2O: Beispiele für dodekaedrische und quadratisch-antiprismatische Achterkoordination

Crystal Structures of Octacyanomolybdates(IV). III (NMe₄)₃Li[Mo(CN)₈] · 3.5 H₂O and Cs₇Na[Mo(CN)₈]₂ · 4.17 H₂O: Examples of Dodecahedral and Square Antiprismatic Eight-Coordination At single crystals of the hydrated tetragonal cyano complexes (NMe₄)₃Li[Mo(CN)₈] · 3.5 H₂O (a = 1707.5(3), c = 1054.9(2) pm, space group P42₁m, Z = 4) and Cs₇Na[Mo(CN)₈]₂ · 4.17 H₂O (a = 1547.9(1), c = 3254.6(6) pm, I4₁/a, Z = 8) X-ray structure determinations were performed. The [Mo(CN)₈]^4– polyhedra agree with respect to their mean distances Mo–C and C–N (216,7/114,3 pm resp. 216,1/114,7 pm) within their standard deviations, however, there is a distorted dodecahedron in the first case ((NMe₄)₃Li-complex), and a distorted square antiprism in the second (Cs₇Na-complex). The coordination of the counter cations, partly hydrated, the formation of hydrogen bridges and the packing of the complex anions is discussed.     

Synthese und Struktur von [(Ph3PAu)6Co(CO)2](PF6) und [(Ph3PAu)7Co(CO)2](PF6)2

Synthesis and Structure of [(Ph₃PAu)₆Co(CO)₂](PF₆) and [(Ph₃PAu)₇Co(CO)₂](PF₆)₂ By the reaction of (Ph₃PAu)₄Co[(CO)₃]⁺ with OH^? in the presence of excess Ph₃PAuCl the larger cluster cations [(Ph₃PAu)₆Co(CO)₂]⁺ ( 1 ) and [(Ph₃PAu)₇Co(CO)₂]²⁺ ( 2 ) can be built up with 1 being the main product. 1 crystallizes with PF^?₆ as counterion in the monoclinic space group C2/c with a = 3008.3(6); b = 1339.1(2); c = 2909.4(6) pm; β = 103.08(1)°; Z = 4. The inner core of the cluster cation 1 with the symmetry C₂ has the form of a bicapped trigonal bipyramid with the heteroatom in equatorial position, and distances Au? Au between 280.4(1) and 288.4(1) pm and Co? Au between 254.9(1) and 257.1(2) pm. 2 · (PF₆)₂ crystallizes in the triclinic space group P1 with a = 2155.7(1); b = 1720.6(1); c = 3543.6(1) pm; α = 91.89(1)°; β = 97.51(1); γ = 89.92(1)°; Z = 4. The unit cell contains two symmetry independent cluster cations 2 of about the same geometry. The cluster skeleton Au₇Co can be described as fragment of an icosahedron formed by seven gold atoms with the Co atom in its center. The Au? Au distances range from 274.8(3) to 332.6(3) pm, and the Co? Au distances are 256.8(6) to 264.7(5) pm. The bonding in 1 and 2 is discussed.     

Chromhexacyano‐Komplexe: Die Kristallstrukturen der Cyanoelpasolithe (NMe4)2ACr(CN)6 (A = K,Cs) und der kubischen Bariumverbindung Ba3[Cr(CN)6]2 · 20 H2O

Chromium Hexacyano Complexes: The Crystal Structures of the Cyano Elpasolites (NMe₄)₂ACr(CN)₆ (A = K, Cs) and of the Cubic Barium Compound Ba₃[Cr(CN)₆]₂ · 20 H₂O The crystal structures of the cyano elpasolites (NMe₄)₂KCr(CN)₆ (a = 1527.3(1), b = 888.1(1), c = 1539.0(1) pm, β = 109.92(1)°; C2/c, Z = 4) and (NMe₄)₂CsCr(CN)₆ (a = 1278.9(1) pm; Fm3m, Z = 4), as well as of the cubic compound Ba₃[Cr(CN)₆]₂ · 20 H₂O (a = 1631.0(1) pm; Im3m, Z = 4) were determined by X‐ray methods with single crystals. Reasons for the enlarged distances within the [Cr(CN)₆]^3–‐octahedron of the K compound (Cr–C: 209.3 pm) compared to the observations within both cubic complexes (206.1 resp. 206.9 pm) are discussed in context with the tolerance factors of cyano elpasolites. As is the case there concerning the cyano bridges Cr–CN–A towards the alkali ions the novel structure type of the barium compound, too, exhibits nearly linear bridging towards Ba. It contributes, however, only four N ligands to the ninefold [BaN₄O₅] coordination; part of the aqua ligands show disorder (Ba–N: 287.5, Ba–O: 281/293 pm).