Synthesis and Multinuclear NMR Study of Benzoyl Methylene Triparatolylphosphorane Ylide and the Reaction of this Ylide with Mercury(II) Halides

The reaction of the title ylide {PhCOCHP(p-tolyl)₃} with Pd(II), Pt(II). Hg(II), and Ag(I) in equimolar ratios using CH₃CN, CH₃OH, and CH₂Cl₂ as solvents have yielded [{(p-tolyl)₃PCHCOC₆H₅} PdCl₂]₂ (I), [{(p-tolyl)₃ PCHCOC₆H₅} PtCl₂]₂(2), [Hg(NO₃)₂ {(p-tolyl)₃ PCHCOC₆H₅}](3), and [Ag{(p-tolyl)₃ PCHCOC₆H₅ < eqid1 > ₂]⁺ (4). The IR, ¹H ¹³C, and ³¹P NMR together with micro analysis data of the products were obtained.     

Synthesis,spectroscopic and X-ray structural studies of mercury(II) halide complexes of 4-methoxybenzoylmethylenetriphenylphosphorane

The reactions of the title ylide {(C₆H₅)₃PCHCOC₆H₄OCH₃)} (MBPPY) with mercury(II) chloride and mercury(II) bromide in equimolar ratios using methanol as the solvent produces crystals of [(MBPPY) · HgCl₂]₂ (1) and [(MBPPY) · HgBr₂]₂ (2), respectively. Single crystal X-ray analyses reveal the presence of centrosymmetric dimeric structures containing the ylide and HgX₂ (X = Cl or Br) in both cases. The IR and NMR data of the product [(MBPPY) · HgI₂]₂ (3), formed by the reaction of mercury(II) iodide with the same ylide, are similar to those of 1 and 2. Analytical data indicate a 1:1 stoichiometry between the ylide and Hg(II) halide in each of the three products.     

Charakterisierung von Distorsionsisomeren der Anionen Pentacyano-oxo-molybdat(IV) sowie Tetracyano-oxo-aqua-molybdat(IV) im festen Zustand. Kristallstrukturen von [(C6H5)4P]3[MoO(CN)5] · 7 H2O(grün), [(C6H5)4As]2 [MoO(OH2)(CN)4] · 4 H2O (blau) und [(C6H5)4P]2[MoO(OH2)(CN)4] · 4 H2O (grün)

Characterization of Distortional Isomers of the Anions Pentacyano-oxo-molybdate(IV) and of Tetracyano-aqua-oxo-molybdate(IV) in the Solid State. Crystal Structures of [(C₆H₅)₄P]₃[MoO(CN)₅] · 7 H₂O (green), [(C₆H₅)₄As]₂[MoO(OH₂)(CN)₄] · 4 H₂O (blue), and [(C₆H₅)₄P]₂[MoO(OH₂) (CN)₄] · 4 H₂O (green) Preparation of a series of salts containing the new pentacyano-oxo-molybdate(IV) anion is described: Cs₂H[MoO(CN)₅] (blue), [(CH₃)₄N]₂H[MoO(CN)₅] · 2 H₂O (blue) and [Cr(en)₃] [MoO(CN)₅] · 4 H₂O (green). The green [(C₆H₅)₄P]₃[MoO(CN)₅] · 7 H₂O crystallizes triclinic in the space group P1 . The molybdenum(IV) center is in an pseudo-octahedral environment of a terminal oxo-group (d(Mo?O); 1.705(4) Å), a CN^? group in the trans-position (d(Mo? C): 2.373(6) Å), and four equatorial CN^? groups (averaged d(Mo? C): 2.178 (Å). The blue and green salts exhibit v(Mo?O) stretching frequencies at 948 cm^?1 and 920 cm^?1, respectively. Blue and green salts containing the [MoO(OH₂)(CN)₄]^2? anion and [(C₆H₅)₄P]⁺ or [(C₆H₅)₄As]⁺ cations have been prepared and characterized by single crystal crystallography. [(C₆H₅)₄P]₂[MoO(OH₂)(CN)₄] · 4 H₂O (green) and [(C₆H₅)₄As]₂[MoO(OH₂)(CN)₄] · 4 H₂O (blue) crystallize monoclinic in the space group C—P2₁/n. They are considered to be distortional isomers of the complex anion: the green species has a Mo?O bond distance of 1.72(2) Å whereas for the blue species d(Mo?O) = 1.60(2) Å is found; the corresponding v(Mo?O) frequencies are at 920 cm^?1 and 980 cm^?1.     

Neue Benzylkomplexe der Lanthanoiden. Darstellung und Kristallstrukturen von [(C5Me5)2Y(CH2C6H5)(thf)], [(C5Me5)2Sm(CH2C6H5)2K(thf)2]∞ und [(C5Me5)Gd(CH2C6H5)2(thf)]

New Benzyl Complexes of the Lanthanides. Synthesis and Crystal Structures of [(C₅Me₅)₂Y(CH₂C₆H₅)(thf)], [(C₅Me₅)₂Sm(CH₂C₆H₅)₂K(thf)₂]_∞, and [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] YBr₃ reacts with potassium benzyl and [K(C₅Me₅)] in THF to give KBr and the monobenzyl compound [(C₅Me₅)₂ · Y(CH₂C₆H₅)(thf)] 1 . The analogous reaction with SmBr₃ in THF leads to the polymeric product [(C₅Me₅)₂Sm(CH₂C₆H₅)₂ ∞ K(thf)₂]_∞ 2 , with GdBr₃ to [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] 3 . The structures of 1–3 were determined by X-ray single crystal structure analysis:

• Space group P1 , Z = 2, a = 851.2(4) pm, b = 952.7(4) pm, c = 1858.6(8) pm, α = 79.90(4)°, β = 77.35(4)°, γ = 73.30(3)°.
• Space group P1 , Z = 2, a = 903.3(2) pm, b = 1375.9(3) pm, c = 1801.1(4) pm, α = 100.92(3)°, β = 100.77°, γ = 98.25(3)°.
• Space group P2₁/n, Z = 8, a = 1458.2(5) pm, b = 927.8(3) pm, c = 3792.9(15) pm, β = 96.83(3)°.

     

[(C6H10)(NH3)2][Ni(H2O)4C6H2(COO)4]·4H2O – A Coordination Polymer with the Chain‐like Polyanion {Ni(H2O)4[C6H2(COO)4]2−}n

Triclinic single crystals of [(C₆H₁₀)(NH₃)₂][Ni(H₂O)₄C₆H₂(COO)₄]·4H₂O have been prepared in aqueous solution at 55 °C. Space group (Nr. 2), a = 691.23(6), b = 924.84(5), c = 1082.43(7) pm, α = 74.208(6)°, β = 75.558(7)°, γ = 68.251(6)°, V = 0.60985(7) nm³, Z = 1. The Nickel(II) species, located on a crystallographic inversion centre, is coordinated in a trans‐octahedral fashion by two oxygen atoms stemming from the centrosymmetric pyromellitate anions and four from water molecules (Ni–O 205.82(12) – 208.11(13) pm). The connection between Ni²⁺ and [C₆H₂(COO)₄)]^4? leads to infinite chain‐like polyanions extending parallel to with {Ni(H₂O)₄[C₆H₂(COO)₄]^2?}_n composition. [(C₆H₁₀)(NH₃)₂]²⁺‐cations are accomodated between the chains, compensating for the negative charge of the polyanions. Thermogravimetric analysis in air showed that the loss of water of crystallisation occurs in two steps between 102 and 206 °C, corresponding to the loss of 6 and 2 water molecules per formula unit, respectively. The dehydrated sample was stable between 206 and 353 °C. Further decomposition yielded nickel(II) oxide (NiO).     

Synthese und Struktur von [(Ph3C6H2)Te]2, [(Ph3C6H2)Te(AuPPh3)2]PF6 und [(Ph3C6H2)TeAuI2]2

Synthesis and Structure of [(Ph₃C₆H₂)Te]₂, [(Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ and [(Ph₃C₆H₂)TeAuI₂]₂ [(2,4,6-Ph₃C₆H₂)Te]₂ reacts with Ph₃PAu⁺ to yield [2,4,6-Ph₃C₆H₂TeAuPPh₃₂]PF₆ which can be oxidized by I₂ to form the gold(III) complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂. [(2,4,6-Ph₃C₆H₂)Te]₂ crystallizes in the monoclinic space group P2₁/c with a = 810.6(2); b = 2026.5(5); c = 2260.6(7) pm; β = 99.23(3)° and Z = 4. In the crystal structure the ditelluride exhibits a dihedral angle C11? Te1? Te2? C21 of 66.1(2)°. The distance Te1? Te2 is 269.45(6) pm. In the cation of the triclinic complex [(2,4,6-Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ (space group P1 ; a = 1197.4(3); b = 1457.2(4); c = 1680.0(6) pm; α = 84.69(3)°; β = 85.11(3)°; γ = 75.54(3)°; Z = 2) a pyramidal skeleton RTeAu₂ with distances Te? Au = 259.2(1) and 257.8(2) pm and Au? Au = 295.3(1) pm is present. [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ crystallizes in the triclinic space group P1 with a = 1086.3(3); b = 1462.9(6); c = 1654.2(2) pm; α = 85.25(2)°; β = 87.44(1)°; γ = 80.90(3)°; Z = 2. In the centrosymmetrical dinuclear complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ the Au atoms exhibit a square-planar coordination by two iodine atoms and two tellurolate ligands. The tellurolate ligands form symmetrical bridges with distances Te? Au = 260.0 pm. The distances Au? I are in the range of 260.3(1) and 263.7(1) pm.     

Kristallstrukturen der Fluorochloroplatinate(IV) cis-[(C5H5N)2CH2][PtF4Cl2], trans-[(C5H5N)2CH2][PtF4Cl2] · H2O und [(C5H5N)2CH2][PtF5Cl]

Crystal Structures of the Fluorochloroplatinates(IV) cis-[(C₅H₅N)₂CH₂][PtF₄Cl₂], trans-[(C₅H₅N)₂CH₂][PtF₄Cl₂] · H₂O, and [(C₅H₅N)₂CH₂][PtF₅Cl] The complex ions cis-[PtF₄Cl₂]^2?, trans-[PtF₄Cl₂]^2? and [PtF₅Cl]^2? have been synthesized by stereoselective ligand exchange reactions utilizing the trans effect and are separated by ion exchange chromatography on diethylaminoethyl cellulose. These anions form stable AB-type salts with the doubly charged cation dipyridiniomethane, [(C₅H₅N)₂CH₂]²⁺. X-ray structure determinations on single crystals of cis-[(C₅H₅N)₂CH₂][PtF₄Cl₂] ( 1 ) (monoclinic, space group P2₁/n with a = 10.379(10), b = 9.635(2), c = 13.738(2) Å, β = 99.142(10)°, Z = 4), trans-[(C₅H₅N)₂CH₂][PtF₄Cl₂] · H₂O ( 2 ) (triclinic, space group P1 with a = 7.757(4), b = 10.059(7), c = 10.408(6) Å, α = 82.49(5), β = 68.92(4), γ = 75.46(4)°, Z = 2) and [(C₅H₅N)₂CH₂][PtF₅Cl] ( 3 ) (orthorhombic, space group Pnma with a = 10.394(3), b = 13.320(2), c = 9.2694(10) Å, Z = 4), reveal the perfect ordering of the anion sublattice. The stronger trans influence of Cl compared with F is observed in asymmetric axes $ {\rm F}^ \bullet $? Pt? Cl′. The bond lengths Pt? $ {\rm F}^ \bullet $ are 0.026 Å (1.4%) longer and the Pt? Cl′ distances are 0.078 Å (3,3%) shorter in comparison with those of symmetrically coordinated axes. The weakening of the Pt? $ {\rm F}^ \bullet $ bond and the strengthening of the Pt? Cl′ bond is better recognizable from shifts of the stretching vibrations by 8% to lower and by 13% to higher frequencies, respectively. Correspondingly, the valence force constants are found to be 15% lower and 22% higher. The trans influence is observed most distinctly in the ¹⁹F-nmr spectra exhibiting the coupling constant ¹J($ {\rm F}^ \bullet $Pt) to be 29% smaller than ¹J(FPt).     

Two New Modifications of [P(C6H5)4]2[Cu2I4]

Single crystals of two new modifications of [P(C₆H₅)₄]₂[Cu₂I₄] were obtained by reaction of granulated copper with iodine and [P(C₆H₅)₄]I in dry acetone under nitrogen atmosphere. They crystallise monoclinically, space group P2₁/n (No. 14), a = 11.550(6), b = 7.236(2), c = 27.232(13) Å, β = 98.13(3)°, V = 2253(2) ų, and Z = 2 ([P(C₆H₅)₄]₂[Cu₂I₄]-C), and space group Cc (No. 9), a = 17.133(5), b = 15.941(5), c = 18.762 (6) Å, β = 114.02(1)°, V = 4681(3) ų, and Z = 4 ([P(C₆H₅)₄]₂[Cu₂I₄]-D), respectively. In these compounds the [CuI₂]^? anions form dimers di-μ-iodo-diiodocuprate(I), which are either planar ( C ) or folded ( D ).     

Darstellung,spektroskopische Charakterisierung und Kristallstrukturen von [(C5H5N)2CH2][PtCl5(SCN)] und cis-[(C5H5N)2CH2][PtCl4(SCN)2]

Preparation, Spectroscopic Characterization, and Crystal Structures of [(C₅H₅N)₂CH₂][PtCl₅(SCN)] and cis -[(C₅H₅N)₂CH₂][PtCl₄(SCN)₂] By treatment of [PtCl₆]^2– with SCN^– in aqueous solution a mixture of chlorothiocyanatoplatinates(IV) is formed, from which [PtCl₅(SCN)]^2– and cis-[PtCl₄(SCN)₂]^2– have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-Ray structure determinations on single crystals of [(C₅H₅N)₂CH₂][PtCl₅(SCN)] ( 1 ) (tetragonal, space group P 4₃, a = 7.687(1), c = 29.698(4), Z = 4) and cis-[(C₅H₅N)₂CH₂][PtCl₄(SCN)₂] ( 2 ) (monoclinic, space group P 2₁/n, a = 11.2467(9), b = 15.0445(10), c = 11.3179(13), β = 92.840(9)°, Z = 4) show, that the thiocyanate groups are coordinated via S atoms with average Pt–S distances of 2.339 Å and Pt–S–C angles of 104.7° up to 107.1°. Using the molecular parameters of the X-ray determinations the low temperature (10 K) IR and Raman spectra have been assigned by normal coordinate analyses. The valence force constants of the S–Pt–Cl˙ axes are f_d(PtS) = 1.81 ( 1 ) and 1.87 ( 2 ), f_d(PtCl ^× ) = 1.77 ( 1 ) and 1.81 ( 2 ), of the Cl–Pt–Cl axes are f_d(PtCl) = 1.93 ( 1 ) and 1.90 mdyn/Å ( 2 ). The ¹⁹⁵Pt NMR spectra from dichlormethane solutions exhibit each one sharp signal at 3975.6 ( 1 ) and 3231.6 ppm ( 2 ), respectively.     

One‐dimensional Cadmium(II) Coordination Polymers: Syntheses and Crystal Structures of [Cd(H2O)3(C5H6O4)]·2H2O,Cd(H2O)2(C6H8O4), and Cd(H2O)2(C8H12O4)

[Cd(H₂O)₃(C₅H₆O₄)]·2H₂O ( 1 ) and Cd(H₂O)₂(C₆H₈O₄) ( 2 ) were prepared from reactions of fresh CdCO₃ precipitate with aqueous solutions of glutaric acid and adipic acid, respectively, while Cd(H₂O)₂(C₈H₁₂O₄) ( 3 ) crystallized in a filtrate obtained from the hydrothermal reaction of CdCl₂·2.5H₂O, suberic acid and H₂O. Compound 1 consists of hydrogen bonded water molecules and linear {[Cd(H₂O)₃](C₅H₆O₄)_2/2} chains, which result from the pentagonal bipyramidally coordinated Cd atoms bridged by bis‐chelating glutarato ligands. In 2 and 3 , the six‐coordinate Cd atoms are bridged by bis‐chelating adipato and suberato ligands into zigzag chains according to {[Cd(H₂O)₃](C₅H₆O₄)_2/2} and {[Cd(H₂O)₂](C₈H₁₂O₄)_2/2}, respectively. The hydrogen bonds between water and the carboxylate oxygen atoms are responsible for the supramolecular assemblies of the zigzag chains into 3D networks. Crystallographic data: ( 1 ) P1¯ (no. 2), a = 8.012(1), b = 8.160(1), c = 8.939(1) Å, α = 82.29(1)°, β = 76.69(1)°, γ = 81.68(1)°, U = 559.6(1) ų, Z = 2; ( 2 ) C2/c (no. 15), a = 16.495(1), b = 5.578(1), c = 11.073(1) Å, β = 95.48(1)°, U = 1014.2(1) ų, Z = 4; ( 3 ) P2/c (no. 13), a = 9.407(2), b = 5.491(1), c = 11.317(2) Å, β = 95.93(3)°, U = 581.4(2) ų, Z = 2.     

Pentaazadienido-Komplexe von Zink,Cadmium und Quecksilber Die Kristallstruktur von [Cd(EtOC6H4-N5-C6H4OEt)2(py)2] und [Hg(tol-N5-tol)2(py)]

Pentaazadienido Complexes of Zinc, Cadmium, and Mercury. The Crystal Structure of [Cd(EtOC₆H₄-N₅-C₆H₄OEt)₂(py)₂] and [Hg(tol-N₅-tol)₂(py)] The pentaazadienido complexes [M(EtOC₆H₄N₅C₆H₄OEt)₂] (M = Zn ( 1 ), Cd ( 2 )) are formed by the reaction of [M(NH₃)₄]²⁺ with [EtOC₆H₄N₅C₆H₄OEt]^? in aqueous ammonia. 2 crystallizes from pyridine as [Cd(EtOC₆H₄N₅C₆H₄OEt)₂py₂] ( 3 ) with the triclinic space group P1 and a = 937.2(2); b = 1422.7(2); c = 2085.5(2) pm; α = 75.28(1)°; β = 94.74(1)°; γ = 99.75(1)°; Z = 2. The central Cd²⁺ ion of 3 exhibits an octahedral coordination by two pyridine ligands in cis arrangement and two (N1, N3)-²⁺ chelating pentaazadienide ions. The reaction of [HgI₄]² with the 1,5-di(tolyl)pentaazadienide anion in aqueous ammonia affords [Hg(p-tol-N₅-tol)₂] ( 4 ), which crystallizes from pyridine in form of [Hg(tol-N₅-tol)₂py] ( 5 ) with the space group P1 and a = 1176.2(4); b = 1203.1(3); c = 1295.6(5) pm; α = 100.77(3)°; β = 110.08(3)°; γ = 94.29(2)°; Z = 2. In 5 the Hg²⁺ cation is threefold coordinated by two monodentate (N3)-η¹ pentaazadienid anions and one pyridine ligand. Within the N₅ chains of the pentaazadienid anions of 3 and 5 localized N? N double bonds are found in the positions N1? N2 and N4? N5 with distances between 125 and 129 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.     

Metal–Heterocyclic thione interactions-15 – reactivity of coordinated thiones of bis(pyridine- 2-thiolato- or 1-oxopyridine- 2-thiones)palladium(II)/platinum(II) towards divalent metal halides: synthesis of polynuclear complexes

Reactions of dinuclear tetrakis(pyridine-2-thiolato)dipalladium(II) or platinum(II), M₂(C₅H₄NS)₄, with divalent metal halides in organic solvents formed compounds of stoichiometry: [M₂(C₅H₄NS)₄·(M′X₂)₂] {M = Pd, M′X₂ = HgCl₂ (1), PtCl₂ (2), CdCl₂ (3); M = Pt, M′X₂ = HgCl₂ (4)}. Similarly, bis(1-oxopyridine-2-thione)-palladium(II)/platinum(II) formed compounds: [M(C₅H₄NOS)₂·M′X₂] {M = Pd, M′X₂ = HgCl₂ (5), HgBr₂ (6), HgI₂ (7), CdCl₂ (8), PtCl₂ (9); M = Pt, M′X₂ = HgBr₂ (10), HgI₂, (11)}. Compounds 1–11 have been characterized using elemental analysis, IR, far-IR, and NMR (¹H, ¹³C) spectroscopy. Coordination to metal centers of M′X₂ occurs via coordinated sulfur. Possible structures are suggested. The crystallization of (5) in dimethyl sulfoxide formed crystals of Pd(C₅H₄NOS)₂ as revealed by X-ray crystallography.     

Replacement of Trimethylamine in Trimethylamine‐trispentafluoroethyl‐borane. Structures of [(C2F5)3BNMe3], [NMe4][(C2F5)3BOH], and K[(C2F5)3BCH2(CO)C6H5]

Trimethylamine‐tris(pentafluoroethyl)borane [(C₂F₅)₃BNMe₃] ( 1 ) reacts at 190 °C with water under displacement of the trimethylamine ligand to yield the hydroxy‐tris(pentafluoroethyl)borate [(C₂F₅)₃BOH]^? ( 2 ). In tributylamine 1 reacts with alkynes HC≡CR to form novel ethynyl‐tris(pentafluoroethyl)borate anions [(C₂F₅)₃BC≡CR]^? – R = C₆H₅ ( 3 ), C₆H₄CH₃ ( 4 ), Si(CH(CH₃)₂)₃ ( 5 ) – in moderate yields. Compound 3 adds water across the triple bond to form the novel anion [(C₂F₅)₃BCH₂(CO)C₆H₅]^? ( 6 ). The structures of [(C₂F₅)₃BNMe₃], [NMe₄][(C₂F₅)₃BOH] and K[(C₂F₅)₃BCH₂(CO)C₆H₅] have been determined by x‐ray crystallography.     

Darstellung und Kristallstrukturen von [P(C6H5)4][1-(NH3)B10H9] und Cs[(NH3)B12H11] · 2CH3OH

Synthesis and Crystal Structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH The reduction of [1-(NO₂)B₁₀H₉]^2? with aluminum in alkaline solution yields [1-(NH₃)B₁₀H₉]^? and by treatment of [B₁₂H₁₂]^2? with hydroxylamine-O-sulfonic acid [(NH₃)B₁₂H₁₁]^? is formed. The crystal structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] (triclinic, space group P1 , a = 7.491(2), b = 13.341(2), c = 14.235(1) Å, α = 68.127(9), β = 81.85(2), γ = 86.860(3)°, Z = 2) and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH (monoclinic, space group P2₁/n, a = 14.570(2), b = 7.796(1), c = 15.076(2) Å, β = 111.801(8)°, Z = 4) reveal for both compounds the bonding of an ammine substituent to the cluster anion.     

Reaction of (η5‐C5H5)Fe(CO)2I with Anionic Bidentate Phosphine Ligands PPh2(o‐C6H4NHLi) or PPh2(o‐C6H4OLi)

The o‐substituted hybrid phenylphosphines, PPh₂(o‐C₆H₄NH₂) and PPh₂(o‐C₆H₄OH), could be deprotonated with LDA or n‐BuLi to yield PPh₂(o‐C₆H₄NHLi) and PPh₂(o‐C₆H₄OLi), respectively. When added to a solution of (η⁵‐C₅H₅)Fe(CO)₂I at room temperature, these two lithiated reagents produce a chelated neutral complex 1 (η⁵‐C₅H₅)Fe(CO)[C(O)NH(o‐C₆H₄)PPh₂‐C,P‐η²] for the former and mainly a zwitterionic complex 2 , (η⁵‐C₅H₅)Fe⁺(CO)₂[PPh₂(o‐C₆H₄O^?)] for the latter. Complex 1 could easily be protonated and then decarbonylated to give 4 [(η⁵‐C₅H₅)Fe(CO){NH₂(o‐C₆H₄)PPh₂‐N,P‐η²}⁺]. Complexes 1 and 4‐I have been crystallographically characterized with X‐ray diffraction.     

m -Terphenyl derivative of titanium(III): Cp2TiR (Cp=C5H5; R =2,6-(4-MeC6H4)2C6H3)

The title compound, Cp₂TiR (Cp=C₅H₅; R=2,6-(4-MeC₆H₄)₂C₆H₃), 1, was prepared by reaction of RLi with [Cp₂TiCl]₂. Compound 1 was characterized by elemental analysis, EPR, and single crystal X-ray crystallography. The title compound crystallizes in the monoclinic space group C2/c with the following unit cell dimensions: a=11.1466(7) Å, b=16.4429(11) Å, c=13.0786(8) Å; b=106.2040(10)^°;V=2301.9(3) ų. The EPR spectrum of 1 displays two signals, a high field signal at g=1.979 and a lower field signal at g=1.959. Significantly, 1 is a sterically encumbered m-terphenyl-stabilized trivalent titanocene paramagnetic complex and may be a practical one-electron reducing reagent.     

Syntheses and crystal structures of [(C6H5CH2C5H4)2GdCl.THF]2 and (C6H5CH2C5H4)2ErCl.THF

[(C₆H₅CH₂C₅H₄)₂GdCl.THF]₂ (1) and (C₆H₅CH₂C₅H₄)₂ErCl.THF (2) were prepared by the reaction of LnCl₃ (Ln? Gd, Er) with benzylcyclopentadienyl sodium in THF and characterized by elemental analysis, IR, ¹H NMR, ¹³C NMR, MS and thermal gravimetry. The crystal structures of both compounds were determined. Complex 1 is dimeric and its structure belongs to the monoclinic, P2₁/c space group with a=1.1432(2), b=1.2978(2), c=1.7604(3) nm, β=108.75(2), V=2.4732(9) nm³, Z=2(four monomers), D_c“1.54 g.cm^?3. R=0.0342 and R_w“0.0362. Complex 2 is monomer and its structure belongs to the orthorhombic, P2₁2₁2₁ space group with a=0.8645(2), b=1.1394(3), c=2.5289(4) nm, V=2.4919(9) nm³, Z=4, D_c“1.56 g.cm^?3. R=0.0514, R_w“0.0529. The determination of the crystal structure shows that in complex 1 the benzyl groups on the cyclopentadienyls coordinated to Gd³⁺ are located in the opposite direction (139°); in complex 2 the benzyl groups on the cyclopentadienyls coordinated to Er³⁺ are located in the same direction (6.5°).     

Complexes of N-Phosphorylated Thioureas RNHC(S)NHP(O)(OiPr)2 (R = 2-MeC6H4, 2,6-Me2C6H3, 2,4,6-Me3C6H2) With Nickel(II)

The reaction of O,O′-diisopropylphosphoric acid isothiocyanate (iPrO)₂P(O)NCS with 2-methylaniline 2-MeC₆H₄NH₂, 2,6-dimethylaniline 2,6-Me₂C₆H₃NH₂, or 2,4,6-trimethylaniline 2,4,6-Me₃C₆H₂NH₂ leads to the N-phosphorylated thioureas RNHC(S)NHP(O)(OiPr)₂ (R = 2-MeC₆H₄?, HL^I ; 2,6-Me₂C₆H₃?, HL^II ; 2,4,6-Me₃C₆H₂?, HL^III ). Reaction of the potassium salts of HL^{I –III} with Ni(II) in aqueous EtOH leads to [Ni(L^I–III-N,S)₂] ([NiL^I–III ₂ ]) chelate complexes. The compounds obtained were investigated by ¹H, ³¹P{¹H} NMR spectroscopy and microanalysis. The molecular structure of the thiourea HL^III was elucidated by single crystal X-ray diffraction analysis. Single crystal X-ray diffraction studies showed that HL^III forms both intra- and intermolecular hydrogen bonds, which in turn leads to the formation of polymeric chains. One of the intermolecular hydrogen bonds is of the type N?H…S. Moreover, the formation of intermolecular C?H…η⁶-phenyl interactions was established.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Bis(arylimido) Molybdenum(VI) Amidinate and Guanidinate Complexes; Molecular Structures of [(ArN)2MoMe{N(Cy)C[N(i‐Pr)2]N(Cy)}] (Ar = 2,6‐i‐Pr2C6H3; Cy = Cyclohexyl) and [(2,6‐i‐Pr2C6H3N)2MoCl2] · [NH=C(C6H5)CH(SiMe3)2]

The reaction of [(ArN)₂MoCl₂] · DME (Ar = 2,6‐i‐Pr₂C₆H₃) ( 1 ) with lithium amidinates or guanidinates resulted in molybdenum(VI) complexes [(ArN)₂MoCl{N(R¹)C(R²)N(R¹)}] (R¹ = Cy (cyclohexyl), R² = Me ( 2 ); R¹ = Cy, R² = N(i‐Pr)₂ ( 3 ); R¹ = Cy, R² = N(SiMe₃)₂ ( 4 ); R¹ = SiMe₃, R² = C₆H₅ ( 5 )) with five coordinated molybdenum atoms. Methylation of these compounds was exemplified by the reactions of 2 and 3 with MeLi affording the corresponding methylates [(ArN)₂MoMe{N(R¹)C(R²)N(R¹)}] (R¹ = Cy, R² = Me ( 6 ); R¹ = Cy, R² = N(i‐Pr)₂ ( 7 )). The analogous reaction of 1 with bulky [N(SiMe₃)C(C₆H₅)C(SiMe₃)₂]Li · THF did not give the corresponding metathesis product, but a Schiff base adduct [(ArN)₂MoCl₂] · [NH=C(C₆H₅)CH(SiMe₃)₂] ( 8 ) in low yield. The molecular structures of 7 and 8 are established by the X‐ray single crystal structural analysis.