Studies on solid state reactions of coordination compounds LI.Solid state syntheses of a family of Ag-Mo(W)-S cubane-like cluster compounds:Crystal structures of{Ag_3MoS_3I}(PPh_3)_3S and{Ag_3WS_3Cl}(PPh_3)_3S·0.5P(S)Ph_3·3H_2O~+

Reactions of[NH_4]_2[MS_4](M=Mo,W),AgX(X=Cl,Br,I,CN,SCN)and PPh_3in the solid state produced six new mixed-metal sulfur containing cluster compounds,two ofwhich,{Ag_3MoS_3I}(PPh_3)_3S(1)and{Ag_3WS_3Cl}(PPh_3)_3S·0.5P(S)Ph_3·3H_2O(2),were determinedby single crystal X-ray analysis.The crystal data:1,triclinic,P,a=12.114(2),b=13.420(2),c=20.346(3),α=74.53(1),β=86.73(1),γ=63.74(1)°,Z=2,R=0.043 for 4805 independentdata;2,hexagonal,R3,a=b=16.201(3),c=45.091(10),Z=6,R=0.042 for 2729 independentdata.The central unit{Ag_3MS_3X}(M=Mo,W;X=Cl,I)of the two compounds can be des-cribed as a slightly distorted cube,four corners being formed by the MS_4~(2-) ligand(with a ter-minal S atom).The remaining corners are occupied by one X(Cl or I)atom and three Agatoms(with one PPh_3 ligand bound to each of the latter).The generation of different types ofAg-Mo(W)-S cluster compounds prepared from solid state reactions under different reactiontemperatues is discussed.     

Syntheses,Crystal Structures and Non‐linear Optical Properties of Cluster Compounds [MoAu2S4(PPh2Py)2] and [WAu2S4(PPh2Py)2]

The cluster compounds, [MoAu₂S₄(PPh₂Py)₂] ( 1 ) and [WAu₂S₄(PPh₂Py)₂] ( 2 ), were synthesized by the reaction of (NH₄)₂MS₄ (M = Mo, W), H[AuCl₄]·4H₂O and diphenyl‐2‐pyridyl‐phosphine (PPh₂Py) in CH₂Cl₂ solution. [MoAu₂S₄(PPh₂Py)₂] crystallizes in the monoclinic space group P2₁/c with a = 18.385(2), b =12.304(1), c = 16.904(2) Å, β =110.722(2)°, and Z = 4. [WAu₂S₄(PPh₂Py)₂] crystallizes in the triclinic space group P‐1 with a = 9.333 (3), b = 10.628(3), c = 19.566(6) Å, α = 89.26(1), β = 80.87(1), γ = 68.85(1)°, and Z = 2. Single crystal X‐ray analysis showed that these two compounds are isostructural, but belong to different space groups. The Mo (W) atom has a slightly distorted tetrahedral coordination, and the two Au atoms are distorted from trigonal planar, the P—Au—M—Au—P chain is nearly linear. Measurement of the nonlinear optical (NLO) properties using the Z‐scan technique with an 8‐ns pulsed laser at 532 nm showed that 1 and 2 possess NLO absorption and effective self‐focusing effect. The effective α₂ and n₂ values of cluster 1 are 5.89 × 10^—12 m · W^—1 and 6.45 × 10^—18 m² · W^—1; the effective α₂ and n₂ values of compound 2 are 4.35 × 10^—11 m · W^—1 and 3.73 × 10^—17 m² · W^—1.     

Studies on solid state reactions of coordination compounds. LXIII. Solid state synthesis of a series of tetranuclear Mo(W)—Ag mixed-metal clusters. Crystal structures of [(n-Bu)4N]3[MoOS3Ag3Br4] and [(n-Bu)4N]3[WS4Ag3Cl4]

A series of tetranuclear Mo(W)-Ag mixed-metal clusters have been synthesized by making use of the solid state reactions of [NH₄]₂[MYS₃](M= Mo, W; Y= O, S), AgX(X= Cl, Br, I) and (n-Bu)₄NX' (X' =Cl, Br), two of which [(n-Bu)₄N]₃[MoOS₃Ag₃Br₄] (1) and [(n-Bu)₄N]₃[WS₄Ag₃Cl₄] ( 2 ) have been structurally characterized by X-ray analysis. The crystal data: 1 , cubic, P4 3m, αequals;12.093(4) Å, Z=1, R =0.076; 2 , cubic, P4 3m, αequals;12.059(2) Å, Z =1, R =0.075. The cluster anion core [Ag₃MS₃X'] of the two compounds can be viewed as a cube in which the four metal atoms and the four non-metal atoms are statistically distributed, respectively. Substitution reaction with PPh₃ ligand is also discussed for this type of tetranuclear clusters.     

Synthesis of a new salt containing polyoxometallate anion and M?Cu?S cluster cation [MS4Cu4(γ-MePy)8][M6O19] (M = Mo,W). Crystal structure of [WS4Cu4(γ-MePy)8] [W6O19]

Reactions of (NH₄)₂MS₄, AgBr and CuBr in γ-methylpyridine produced one new compound, [MS₄Cu₄(γ-MePy)8][M₆O₁₉] (1, M = W; 2 , M = Mo), of which 1 was characterized by single crystal X-ray analysis. The crystal data: orthorhombic, Pbcn, a = 15.434(4), b = 16.732(2), c = 28.657(7) Å, V = 7400.8(8) ų, Z = 4 , R = 0.072 for 3121 independent data. The compound is the first example which contains both polyoxotungstate anion and heteropolynuclear cluster cation. In the structure of the cation four edges of the tetrahedral WS^2?₄ core are coordinated by four copper atoms, giving a WS₄Cu₄ aggregate of approximate D_2h symmetry. The differences between the reaction of Cu⁺ with MS^2?₄ and that of Ag+ with MS^2?₄ in pyridine and its derivatives are discussed.     

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)°.     

Reaction of small molecules O2, NO,CO, and the Naldini salt (PPh3)2MnBr2: Characterized by infrared spectroscopy,elemental analysis,and single-crystal X-ray diffraction

Addition of 2 equiv. of PPh₃ to MnBr₂ in tetrahydrofuran (THF) solution under N₂ atmosphere results in the formation of Naldini salt (PPh₃)₂MnBr₂ ( 1 ). Reaction of Complex 1 and O₂, NO, and CO (with reducing agent) leads to Complex (OPPh₃)₂MnBr₂ ( 2 ), (PPh₃)₂Mn(NO)Br₂ ( 3 ), and (PPh₃)₂Mn(CO)₃Br ( 4 ), respectively. Both Complexes 2 and 4 crystallize in the triclinic space group P-1 with a = 9.94 Å, b = 10.11 Å, c = 10.53 Å; α = 65.42°, β = 63.16°, and γ = 89.22° of 2 and a = 10.23 Å, b = 12.26 Å, c = 14.44 Å and α = 97.03°, β = 104.34°, and γ = 106.33° of 4 . The isoelectronic replacement of 3CO with 2NO yields the {Mn(NO)₂}⁸ species (PPh₃)₂Mn(NO)₂Br ( 5 ). The single crystal of 5 is in the monoclinic space group C2/c with a = 23.17 Å, b = 9.62 Å, c = 15.92 Å, and β = 114.91°. In the THF solution, Complex 5 serves as an NO source in the presence of NO trapping, Co(TPP), Co(TPP) = 5,10,15,20-tetraphenyl-21H,23H-porphine cobalt(II).     

Sulfur‐assisted Chloride and Triphenylphosphine Dissociation of Palladium(II) Complex with Phenyloxythiocarbonyl,PhOC(S), Containing Ligand: X‐Ray Structure of [Pd(PPh3)2{η1‐C(S)OPh}(Cl)]

Treatment of Pd(PPh₃)₄ with phenylchlorothionoformate, PhOC(S)Cl, in dichloromethane at ?20 °C produces the phenyloxythiocarbonyl complex [Pd(PPh₃)₂{η¹‐C(S)OPh}(Cl)], 1 . The ³¹P{¹H} NMR spectrum of 1 shows the dissociation of either the chloride or the triphenylphosphine ligand to form complex [Pd(PPh₃)₂(η²‐SCOPh)][Cl], 2 or the dipalladium complex [Pd(PPh₃)Cl]₂(μ,η²‐SCOPh)₂, 3 . Continuous stirring of the dichloromethane solution of 1 at room temperature for 4 h forms the dipalladinum complex [Pd(PPh₃)Cl]₂(μ,η²‐SCOPh)₂, 3 as the final product. Respective reactions of 1 and Et₂NCS₂Na or dppa {bis(diphenylphosphino)amine} gives complex [Pd(PPh₃){η¹‐C(S)OPh}(η²‐S₂CNEt₂)], 4 or [Pd(PPh₃){η¹‐C(S)OPh}(η²‐dppa)][Cl], 5 . Complex 1 is determined by single‐crystal X‐ray diffraction and crystallized in the monoclinic space group P2₁ with Z = 4. The cell dimensions of 1 are as follows: a = 9.5613(1) Å, b = 33.6732(3) Å, c = 12.2979(1) Å.     

Direct Syntheses of Bis(tetraphenylphosphonium) and Bis(ethyltriphenylphosphonium) Hexabromo‐diselenates(II), [PPh4]2[Se2Br6] and [PEtPh3]2[Se2Br6]. The Crystal Structure of [PEtPh3]2[Se2Br6]

Brown crystals of [PPh₄]₂[Se₂Br₆] ( 1 ) and [PEtPh₃]₂[Se₂Br₆] ( 2 ) were obtained when selenium and bromine reacted in acetonitrile solution in the presence of tetraphenylphosphonium bromide and ethyltriphenylphosphonium bromide, respectively. The crystal structure of 2 has been determined by X‐ray methods and refined to R = 0.0420 for 4161 reflections. The crystals are monoclinic, space group P2₁/n with Z = 2 and a = 13.055(3) Å, b = 12.628(3) Å, c = 13.530(3) Å, β = 92.40(3)° (293(2) K). In the solid state structure of 2 the dinuclear hexabromo‐diselenate(II) anion is centrosymmetric and consists of two distorted almost square‐planar SeBr₄ units sharing a common edge through two bridging Br atoms. The terminal Se^II–Br bond distances are found to be 2.419(1) and 2.445(1) Å, the bridging μBr–Se^II bond distances 2.901(1) and 2.802(1) Å.     

Darstellung der Halogeno-Pyridin-Rhenate(III), [ReX6−n (Py)n](3−n)− (X = Br,Cl; n = 1−3), sowie Kristallstrukturen von trans-[(C4H9)4N][ReBr4(Py)2], mer-[ReCl3(Py)3] und mer-[ReBr3(Py)3]

Preparation of Halogeno Pyridine Rhenates(III), [ReX_6?n(Py)_n]^(3?n)? (X = Br, Cl; n = 1?3) Crystal Structures of trans-[(C₄H₉)₄N][ReBr₄(Py)₂], mer-[ReCl₃(Py)₃], and mer- [ReBr₃(Py)₃] The mixed halogeno-pyridine-rhenates(III), [ReX_6?n(Py)_n]^(3?n)? (X = Br, Cl), n = 1?3, have been prepared for the first time by reaction of the tetrabutylammoniumsalts (TBA)₂[ReX₆] (X = Br, Cl) in pyridine with (TBA)BH₄ and separation by chromatography on Al₂O₃. Apart from the monopyridine complexes only the trans and mer isomers are formed from the bis-and tris-pyridine compounds. The X-ray structure determinations of the isotypic neutral complexes mer- [ReX₃(Py)₃] (monoclinic, space group P 2₁/n, Z = 4; for X = Cl: a = 9,1120(8), b = 12,5156(14), c = 15,6100(13) Å, β = 91,385(7)°; for X = Br: a = 9,152(5), b = 12,852(13), c = 15,669(2) Å, β = 90,43(2)°) reveal, due to the stronger trans influence of pyridine compared with Cl and Br, that the Re? X distances in asymmetric Py? Re? X3 axes with ReCl3 = 2,397 Å and ReBr3 = 2,534 Å are elongated by 1,3 and 1% in comparison with symmetric X1? Re? X2 axes with ReCl1 = ReCl2 = 2,367 Å and ReBr1 = 2,513 and ReBr2 = 2,506 Å, respectively. The Re? N bond lengths are roughly equal with 2,12 Å. Trans-(TBA)[ReBr₄(Py)₂] crystallizes triclinic, space group P1 , a = 9,2048(12), b = 12,0792(11), c = 15,525(2) Å, α = 95,239(10), β = 94,193(11), γ = 106,153(9)°, Z = 2. The unit cell contains two independent but very similar complex anions with approximate D_2h(mmm) point symmetry.     

Synthetic and structural chemistry of nickel(II) complexes containing dithiolato and phosphine ligands I. Preparation and crystal structure of Ni2(PPh3)2(edt)2

A nickel(II) complex containing both dithiolato and phosphine ligands, Ni₂(PPh₃)₂(edt)₂ (edt = SCH₂CH₂S^2-), has been prepared and characterized by X-ray diffration. The complex crystallizes in the triclinic system, space group P-1, with a = 10.693(3), b = 17.457 (6), c = 10.606 (3) Å, α = 102.84(2), β = 96.49 (2), γ = 82.56(3); V = 1906.8 ų; D_c = 1.439 g·cm^?3 for Z = 2; the final conventional R was 0.052 based on 3338 observed reflections. Nickel atoms are linked by two sulfur atoms from two edt ligands with the Ni—Ni distance of 2.893 Å, and each Ni atom is coordinated by one phosphorus atom and three sulfur atoms with a square-planar geometry, where the average length of Ni—S bond is 2.180 Å and Ni—P bond 2.188 Å. The UV-Vis and ¹H NMR spectra have also been recorded.     

Synthesis and structure of the cluster μ3-sulfido-μ-–(diethylphosphorodithioato-S,S'-)-allylthioureocyclo-tris-[ (μ-sulfido)-χ-(diethylphosphorodithioato-S,S')-molybdenum(IV)], Mo3S4(C4H10O2S2P)4(C4H8N2S)

Title compound, M_r =1273.16, was synthesized by a substitution reaction and its crystal is triclinic belonging to space group P1 with cell parameters: a =13.944(2), b =14.143(7), c =14.233(3) Å, α =77.35(3)°, β =69.94(2)°, γ =63.50(3)°, V=2351(1) ų, Z=2, D_c =1.799g cm^?2. Room temperature, graphite-filtered Mo K_α radiation (λ =0.71073Å) was used for data collection. μ =14.988 cm^?1, F(000) =1280, R=0.051 for 7025 observed reflections. The crystal consists of decrete cluster molecules containing a cluster core [Mo₂(μ₃-S)]¹⁰⁺ with three μ-S, one μ-dtp(dtp =[S₂P(OC₂H₅)]^2-), three χ-dtp and one allylthioureo to form a local six-coordinated sphere around each Mo atom. The bonds of cluster skeleton [Mo₃(μ₃-S)(μ-S)₃]⁴⁺, Mo? Mo 2.744～2.766, Mo—(μ₂-S) 2.340～2.342 and Mo—(μ-S)2.272～2.296 Å, are comparable with those found in the related analogues.     

Facile Synthesis and Molecular Structure of [Ni(PPh2NHPh)4]

NiCl₂ · 6 H₂O readily reacts with PPh₂NHPh in the presence of zinc dust to yield the homoleptic nickel(0) tetrakis‐phosphine complex [Ni(PPh₂NHPh)₄] ( 1 ). 1 crystallises triclinic P1 (no. 2), with a = 14.656(1), b = 17.124(2), c = 17.424(1) Å, α = 95.998(1), β = 111.845(1), γ = 111.402(1)°, V = 3630.04(5) ų, Z = 2, R values [I > 2σ(I)]: R1 = 0.0554, all data: wR2 = 0.1720. The nickel atom is coordinated in a distorted tetrahedral fashion by four phosphorus atoms, resembling a compressed tetrahedron along one of the non‐crystallographic S₄ axes.     

Research on in part “loosely” coordinated trinuclear molybdenum cluster compounds — the synthesis and crystal structure of {Mo3(μ3-S)(μ-S)3[S2P(OEt)2]4 ṁ P(C6H5)3} (0.86CH2Cl2)

The synthesis and crystal structure of novel trinuclear molybdenum cluster compound with somewhat “loose” coordination site {Mo₃(μ₃-S)(μ-S)₃[S₂P(OEt)₂l₄ ? P(C₆H₅)₃} ? (0.86 CH₂C1₂) have been reported. The cluster crystallizes in the space group with two molecules in a unit cell whose parameters are a=10.472(4), b=14.375(2), c=21.695(3)Å; α=74.04(1)°, β=76.50(2)°, γ=72.22 (2)°, V=2950ų and D_o=1.693 g ? cm^?3. On the basis of 4840 independent reflections with I≥2σ(I), the structure was solved by heavy atom method and Fourier method and refined by full-matrix least-squares techniques to a final R=0.058. The distances between Mo atoms in this cluster are 2.731(1), 2.748(1) and 2.753(1)Å respectively. The meat value of Mo—Mo bond lengths is slightly shorter than those in other trinuclear Mo clusters with “loosely coordinated” site. In addition, the PPh₃ ligand is loosely coordinated to one Mo atom in direction opposite to the μ₃-S with Mo—P bond length of 2.647(3)Å. This is different from the other structurally analogous clusters, in which the loosely coordinated ligand is trans to μ₂-S. A summary of Mo—Mo and Mo—L bonding for such clusters is given.     

PPh4[As3S3Cl4] und PPh4[As3S3Br4]

PPh₄[As₃S₃Cl₄] and PPh₄[As₃S₃Br₄] When As₂S₃ reacts with PPh₄X and HX in 1,2-C₂H₄X₂ (X = Cl, Br), the title compounds are obtained as minor products; the main products are PPh₄[As₂SX₅]. Their crystal structures were determined by X-ray diffraction. PPh₄[As₃S₃Cl₄]: a = 1187.7, b = 1090.9, c = 1191.8 pm, α = 82.91, β = 88,93, γ = 88.52°; twins with twin plane (100); R = 0.109 for 1618 observed reflexions of one twin crystal. PPh₄[As₃S₃Br₄]: a = 1119.7, b = 1177.5, c = 1204.1 pm, α = 81.59, β = 85.88, γ = 88.25°; R = 0.061 for 2331 observed reflexions. Both compounds crystallize in the space group P1 , Z = 2, and can be considered to be isotypic. Nevertheless, PPh₄[As₃S₃Br₄] does not form twins as PPh₄[As₃S₃Cl₄]. The crystals consist of PPh₄⁺ and [As₃S₃X₄]^? ions. In the anions, the three As atoms of an As₃S₃ ring in the chair conformation are commonly joined to an X atom and each As atom is bonded to one further terminal X atom. Cations and anions are packed in alternating layers.     

Crystal Structure of the Coordinatively Unsaturated 2-Pyridylphosphine Pd(0) Complex Pd(PPh2Py)3

The three-coordinate tris(2-pyridylphosphine)palladium(0) complex is the first example of a group 10 metal complex bearing pyridine substituted phosphine ligand, whose crystal structure is determined. Pd(PPh₂py)₃ crystallizes in the triclinic space group $ {\rm P}\bar 1 $, with a = 12.874(4) Å, b = 14.162(3) Å, c = 14.912(3) Å, α = 87.76(2)°, β = 66.50(2)°, γ = 63.17(2)°, Z = 2, and V = 2191(1) ų. Full-matrix least-squares refinement of 523 variables using 4911 data (F²_o > 3σF²_o) gave R = 0.033 and R_w = 0.033. The pyridine ring is disordered. Possible weak interactions among Ph rings or Py rings and Pd center are discussed. Close approach of the ortho hydrogen on phenyl rings to the Pd center may imply facile ortho metallation.     

Synthesis,characterization and luminescence of the tetranuclear gold cluster: [Au4{7,8-(PPh2)2-7,8-C2B9H10}2(PPh3)2]

A tetranuclear gold cluster has been synthesized by the reaction of [Au(PPh₃)NO₃] with the closo carborane diphosphine 1,2-(PPh₂)₂-1,2-C₂B₁₀H₁₀ in THF, and characterized by elemental analysis, FT-IR, ¹H and ¹³C?NMR spectroscopy and X-ray structure determination. The cluster crystallizes in the triclinic Pī, a?=?15.118(8)?Å, b?=?16.057(9)?Å, c?=?24.284(13)?Å, α?=?80.822(9)°, β?=?79.624(8)°, γ?=?81.938(8)°, Z?=?2, R ₁?=?0.0626, wR ₂?=?0.1894. A single crystal structure determination showed that four gold atoms form a tetrahedral framework. Among these four gold atoms, two were chelated by two nido carborane diphosphine [7,8-(PPh₂)₂-7,8-C₂B₉H₁₀]^? anions coming from the degradation of the initial closo ligand 1,2-(PPh₂)₂-1,2-C₂B₁₀H₁₀, while the other two were ligated to two PPh₃ groups. The luminescence of this cluster was also investigated in dichloromethane solution at room temperature.     

Syntheses,Structures and Spectroscopic Studies of Quadruply Bonded Complexes Containing Bridging Acetate and η3-etp Ligands (etp = Ph2PCH2CH2P(Ph)CH2CH2PPh2)

The quadruply bonded complexes containing bridging acetate and polydentate phosphine ligands of the type Mo₂(O₂CCR₃)X_J(η³-etp) (R = H, X = Br, 1; R = F, X = CI, 2; R = F, X = Br, 3; etp = Ph₂PCH₂CH₂P(Ph)CH₂CH₂PPh₂) were prepared by reactions of Mo₂(O₂CCR₃)X₂(PPh₃)₂ with etp in CH₂X₂. Their UV-vis and ³¹P{¹H}-NMR spectra have been recorded, and the structure of 1 has been determined by X-ray crystallography. Crystal data for 1·2CH₂Br₂: space group P2₁/c, a = 13.924(7) Å, b = 21.157(4) Å, c = 14.427(5) Å, β = 101.82(3)°, V = 4159(2) ų, Z = 4, with final residuals R = 0.0797 and Rw = 0.0793. The absorption wavelengths of the δ → δ* transitions and the chemical shifts and the coupling constants of the ³¹P{¹H}-NMR spectra of these complexes are dependent on the natures of the halogen atoms and the acetate ligands.     

Synthesis and characterization of [Cu(Phca2en)(PPh3)X] (X=Cl, Br, I, NCS, N3) complexes: crystal structures of [Cu(Phca2en)(PPh3)Br] and [Cu(Phca2en)(PPh3)I]

New mixed-ligand copper(I) complexes, [Cu(Phca₂en)(PPh₃)X], [Phca₂en = N,N′-bis(β-phenylci-nnamaldehyde)-1,2-diiminoethane and X=Cl (1), Br (2), I (3), NCS (4), N₃ (5)] have been synthesized and characterized by various techniques. ¹H and ¹³C-NMR and IR spectral data of these copper(I) complexes are compared with the free ligand to elucidate some structural features. The structures of [Cu(Phca₂en)(PPh₃)Br] (2) and [Cu(Phca₂en)(PPh₃)I] (3) have been determined from single-crystal data showing that the coordination geometry around copper atom is a distorted tetrahedron. Furthermore, these Cu(I) complexes exhibit supramolecular motifs of the type multiple phenyl embraces resulting from attractive interactions between phenyl rings of PPh₃ moieties. The presence of the C–H…Cu weak intramolecular hydrogen bonds, due to the trapping of C–H bonds in the vicinity of the metal atoms, is also reported.     

The Reaction of the Betain‐like Compound O2C2(PPh3)2 with [(cod)PtI2] – Crystal Structure of the Salt (HC{PPh3}2)[(η3‐C8H11)PtI2]

The reaction of the betain‐like compound O₂C₂(PPh₃)₂ ( 1 ) with [(cod)PtX₂] in THF solution gives the salt‐like compounds (HC{PPh₃}₂)[(η³‐C₈H₁₁)PtX₂] ( 3 , X = I; 4 , X = Cl) in about quantitative yields. The new η³‐bonded C₈H₁₁ ligand is the result of a proton transfer from the coordinated cod ligand to 1 with subsequent release of CO₂. The X‐ray analysis of 3 shows the presence of two isomers in a 60:40 ratio, which differ in the bonding of the C₈H₁₁ ligand. 3 crystallizes in the triclinic space group with the unit cell dimensions a = 1091.7(1), b = 1141.5(1), c = 1649.4(2) pm; α = 80.34(1)°, β = 83.62(1)°, γ = 89.03(1)°, V = 2013.7(4)·10⁶ pm³, Z = 2.     

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.