Crystallization of the $${\text{Mn}}^{{\text{II}}}[12{\text{-MC}}_{{\text{Mn}}^{{\text{III}}}{\text{(N)shi}}}{\text{-}}4]^{2+}$$ Mn II [ 12 -MC Mn III (N)shi - 4 ] 2 + Structure with 1,2,4-Triazolate from Methanol

Journal of Chemical Crystallography - The metallacrown (MC) dimer complex {MnII(OAc)(1,2,4-trz) $$[12{\text{-MC}}_{{\text{Mn}}^{{\text{III}}}{\text{(N)shi}}}{\text{-}}4]$$...     

The synthesis and molecular structures of 2,5-diarylpyrroles, [{\text{pyr}}^{{\text{Ar}}_{\text{2}} } ]H (Ar = Ph, 2,4-Xyl)

2,5-Di(2,4-xylyl)pyrrole, H, has been synthesized by reaction of the diketone [XylC(O)CH₂]₂ with NH₄OAc in AcOH; the diketone itself is obtained by condensation of XylC(O)Me with XylC(O)CH₂Br in the presence of Ti(OPrⁱ)₄. The molecular structures of both H and H have been determined by single crystal X-ray diffraction, thereby demonstrating that an ortho methyl substituent increases the dihedral angle between the aryl and pyrrolyl groups from 14.5° in H to 24.1° in H.     

Growth of $${\text{N}}{{{\text{d}}}_{{{\text{1}}\; - \;y}}}{\text{Eu}}_{y}^{{{\text{2}} + }}{{{\text{F}}}_{{{\text{3}}\; - \;y}}}$$ Single Crystals with Tysonite-Type (LaF3) Structure and Investigation of the Concentration Dependence of Some Their Properties

Crystallography Reports - Nd1 – yEuyF3 – y crystals (y is the molar fraction of EuF2; 0 ≤ y ≤ 0.15) with a tysonite (LaF3) structure have...     

Room temperature ligand fragmentation in the reaction between PhCCo3(CO)9 and Ph2PN(Me)N(Me)PPh2. X-ray diffraction structure of PhCCo3(CO)8[Ph2PP(O)Ph2]

The cobalt cluster PhCCo₃(CO)₉ reacts with the bis(phosphanyl)hydrazine ligand bis(diphenylphosphino)dimethylhydrazine (dppdmh) in CH₂Cl₂ with added Me₃NO to give the monosubstituted cluster PhCCo₃(CO)₈[Ph₂PP(O)PPh₂] as the major isolable product. The solid-state structure of this new cluster was unequivocally established by X-ray diffraction analysis, which has confirmed the presence of a noncoordinated (O)PPh₂ moiety. PhCCo₃(CO)₈[Ph₂PP(O)Ph₂] crystallizes in the triclinic space group P , a = 12.036(2), b = 12.037(2), c = 15.124(3) Å, = 84.82(1)°, = 89.44(2)°, = 60.09(1)°, V = 1890.0(6) ų, Z = 2, and d_calc = 1.540 g/cm³.     

Crystal structures of [WI2(CO)3{Ph2P(CH2) n PPh2}] (n = 2 or 3)

[WI₂(CO)₃{Ph₂P(CH₂)₂PPh₂}] (1) crystallizes out in the monoclinic space group P2₁/n, with a = 13.852(7) Å, b = 14.789(19) Å, c = 14.915(19) Å, = 102.86(1)°, Z = 4. [WI₂(CO)₃{Ph₂P(CH₂)₃PPh₂}] (2) crystallizes out in the monoclinic space group P2₁/n, with a = 10.499(15) Å, b = 14.58(2) Å, c = 20.75(3) Å, = 103.59(1)°, Z = 4. Both structures show the metal in a seven-coordinate environment with a carbonyl in the unique capping position, two further carbonyls and a phosphorus in the capped face, and two iodides and the second phosphorus in the uncapped face.     

CO substitution in Ru3(CO)12 by 2,3-bis(diphenylphosphino)-N-phenyl-maleimide (bppm). X-ray diffraction structure of Ru2(CO)6(bppm)

The cluster Ru₃(CO)₁₂ reacts with the diphosphine ligand 2,3-bis(diphenylphosphino)-N-phenyl-maleimide (bppm) in toluene solution at 100C by fragmentation to give a 2:1 mixture of the donor–acceptor complex Ru₂(CO)₆(-bppm) and the phosphido-bridged species Ru₂(CO)₆ , respectively. The new diruthenium compounds have been isolated by chromatography and characterized in solution by IR and NMR (¹H and ³¹P) spectroscopies, in addition to X-ray diffraction analysis in the case of Ru₂(CO)₆( ₂ -bppm). Ru₂(CO)₆( ₂ -bppm), which exists as two crystallographically independent molecules in the unit cell, crystallizes in the orthorhombic space group Pbca, a = 18.8441(9), b = 21.352(2), c = 36.510(2) Å, V = 14,690(1) ų, z = 16, D _calc = 1.649 g/cm³; R = 0.0356, and R _w = 0.0812 for 17732 observed reflections. The reactivity of the bis(diphenylphosphino)-N-phenyl-maleimide ligand with Ru₃(CO)₁₂ under thermolysis conditions is contrasted with the related diphosphine ligands 2,3-bis(diphenylphosphino)maleic anhydride (bma) and 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd).     

Chlorine-atom abstraction and cluster fragmentation in the reaction of H3Re3(CO)10(MeCN)2 with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd): X-ray diffraction structure of fac-ClRe(CO)3(bpcd)

Treatment of the activated trirhenium cluster H₃Re₃(CO)₁₀(MeCN)₂ with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) in CH₂Cl₂ does not afford the expected cluster product H₃Re₃(CO)₁₀(bpcd) but rather the mononuclear complex fac-ClRe(CO)₃(bpcd). The identity of fac-ClRe(CO)₃(bpcd) was determined in solution by IR and NMR (¹H and ³¹P) spectroscopies and the solid-state structure was established by X-ray diffraction analysis. fac-ClRe(CO)₃(bpcd) crystallizes in the triclinic space P-1, a = 9.958(2) Å, b = 11.991(3) Å, c = 13.676(3) Å, α = 73.230(4)°, β = 73.806(4)°, γ = 77.409(4)°, V = 1484.6(6) ų, Z = 2, and d _calc = 1.723 Mg/m³; R = 0.0367, R _w  = 0.0857 for 4253 reflections with I > 2σ(l).     

Ligand substitution in the halo-bridged diruthenium compound [Ru(CO)3Cl2]2 by 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd). Synthesis, spectral properties, and X-ray diffraction structures of cis(CO), trans(Cl)-RuCl2(CO)2 (bpcd) and cis(CO)-RuCl[C(O)Et](CO)2(bpcd)

The reaction between 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) and the chlorobridged diruthenium complex [Ru(CO)₃Cl₂]₂ (1) proceeds readily at room temperature in CH₂Cl₂ to give the new ruthenium compounds cis(CO),trans(Cl)-RuCl₂(CO)₂(bpcd) (2) and cis(CO)-RuCl[C(O)Et](CO)₂(bpcd) (3) as the major and minor products, respectively. Compound 2 was isolated and fully characterized in solution, and the molecular structure was established by X-ray diffraction analysis. cis(CO),trans(Cl)-RuCl₂(CO)₂(bpcd) crystallizes in the triclinic space P-1, a = 9.931(5) Å, b = 12.093(7) Å, c = 13.529(7) Å, α = 72.886(9)°, β = 74.739(9)°, γ = 76.851(9)°, V = 1478.2(1) ų, Z = 2, and d _calc = 1.556 mg/m³; R = 0.0841, R _w = 0.1880 for 4137 reflections with I > 2σ(I). The chlorine atoms in 2 adopt a trans geometry at the octahedral ruthenium center, with the two CO groups exhibiting a cis orientation and trans to the bpcd ligand. cis(CO)–RuCl[C(O)Et](CO)₂(bpcd) crystallizes as two independent molecules in the unit cell in the triclinic space P-1, a = 9.941(2) Å, b = 14.867(2) Å, c = 22.414(3) Å, α = 80.257(3)°, β = 84.796(2)°, γ = 75.207(3)°, V = 3152.6(8) ų, Z = 4, and d _calc = 1.504 mg/m³; R = 0.0428, R _w = 0.0962 for 8242 reflections with I > 2σ(I). The two CO groups are situated cis to each and are opposite to chlorine and phosphine moieties. The production of the minor propionyl compound 3 is discussed with respect to the trace amount of EtOH that is present in the CHCl₃ solvent that is used in the preparation of [Ru(CO)₃Cl₂]₂.     

Ligand-induced polyhedral opening in the mixed-metal cluster MeCCo2NiCp(CO)6 by 4,5-Bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd): X-ray structure of Co2NiCp(CO)4[μ2,η2,η1-C(Me)C=C(PPh2)C(O)CH2C(O)](μ2-PPh2)

The mixed-metal cluster MeCCo₂NiCp(CO)₆ (1) reacts with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) in refluxing CH₂Cl₂ to afford the disubstituted cluster MeCCo₂NiCp(CO)₄(bpcd) (2), which exists as a 1:1 mixture of bridging and chelating bpcd isomers. VT ³¹P NMR spectroscopy confirms that the two bpcd isomers do not interconvert in solution over the temperature range of 182–298 K. Thermolysis of cluster 2 leads to bpcd/cluster activation and formation of the phosphido-bridged cluster Co₂NiCp(CO)₄[μ₂,η²,η¹-C(Me)C=C(PPh₂)C(O)CH₂C(O)](μ₂-PPh₂) (3). The ligand-induced polyhedral expansion that accompanies the formation of the title cluster was established by X-ray diffraction analysis. Co₂NiCp(CO)₄[μ₂,η²,η¹-C(Me)C=C(PPh₂)C(O)CH₂C(O)](μ₂-PPh₂) crystallizes in the triclinic space group P-1, a=9.679(2), b=11.691(2), c=16.653(3) ?, α=85.849(3)°, β=85.456(4)°, γ=66.453(3)°, V=1720.3(6) A³, Z=2, D _cacl=1.632 Mg/m³; R=0.0874, R _w=0.1998 for 7053 observed reflections with I > 2σ(I).