Anne Irving

Deceptively simple Pt complexes of N, N-dialkyl-N′-benzoylthiourea: a 1H, 13C and 195Pt NMR study of their acid-base chemistry in solution and the molecular structure of cis-bis(N, N′-di(n-butyl)-N′-benzoylthioureato)platinum(II)

N,N-Di(n-butyl)-N′-benzoylthiourea readily reacts with PtX42− to yield neutral cis-[PtL2] complexes for X = Cl− and Br−, while for X = I−, the protonated cis-[Pt(LH)2]I2 complex is isolated. The crystal structure of cis-[PtL2] is reported. In chloroform solution, the neutral cis-[PtL2] complexes may readily be protonated to yield a distribution of cis-[Pt(LH)L]+ and cis-[Pt(LH)2]2+ species which have been characterized by means of high resolution multinuclear NMR. Remarkably the 195Pt chemical shift of the cationic species is strongly dependent on the nature of the uncoordinated anion (Cl−, Br−, I−) present, suggesting tight ion-pair formation in solution.

Synthesis and characterization of some new cobaloximes, including the first members of a new class of heterobimetallic cobaloxime complexes. Crystal structure of [{η6-C6H5CH2Co(DH)2(PY)} Cr(CO)3]

Abstract The mononuclear cobaloxime complex o -[{(py)(DH) 2 CoCH 2 }C 6 H 4 (CH 2 Br)] ( 1 ) has been prepared by the reaction of the appropriate xylene dibromide with an equimolar amount of [Co(DH) 2 (py)Cl] in the presence of sodium borohydride (where DH = monoanion of dimethylglyoxime). The dinuclear xylylene-bridged cobatoximes [Co(DH) 2 (py)] 2 [μ-( m - and p -CH 2 C 6 H 4 CH 2 )] ( 2, 3 ) were obtained similarly from the reaction of the xylene dibromides with two molar equivalents of [Co(DH) 2 (py)Cl]. The heterobimetallic complexes [{η 6 -C 6 H 5 CH 2 Co(DH) 2 (py)}Cr(CO) 3 ] ( 4 ) and [Co(DH) 2 (py)] 2 [μ-{(η 6 - p -CH 2 C 6 H 4 CH 2 )Cr(CO) 3 })] ( 7 ) were prepared from [{η 6 -C 6 H 5 CH 2 Cl}Cr(CO) 3 ] and [{η 6 -p-C 6 H 4 (CH 2 Cl) 2 }Cr(CO) 3 ] ( 6 ) respectively, by similar procedures. The new compounds were characterized by standard spectroscopic methods and the structure of 4 was determined by X-ray crystallography. The CoN(py) and CoC bond lengths in 4 are 2.038(4) and 2.044(4) A, respectively.

C-Cl … π(Ar) Interactions

Abstract Geometry consistent with C-Cl … π(Ar) and C-Cl … π(Cp) interactions is shown to occur from a survey of structures in the Cambridge Structural Database. The C-Cl … π(Ar) and C-Cl … π(Cp) angles vary between about 90° to 180°. These angles are more nearly linear as the perpendicular distance of the chlorine atom from the π-system decreases. Many of the interactions are of the ‘edge’ rather than the centroid type.

C-H⋯π(Ar)⋯Cl-C, C-Cl⋯π(Ar), Cl⋯Cl and other interactions in the crystal structure of 6-benzoyl-2,4-bis(trichloromethyl)-1,3-benzdioxin

The title compound is monoclinic,P21/n,Z=4,a=9.934(1),b=18.399(2),c=11.098(2)Å, β=111.08(1)°. The molecule can conveniently be visualized as a benzophenone molecule with one of the aromatic rings fused to a 1,3-dioxin ring which adopts a distorted envelope conformation withcis-trichloromethyl groups substituted at positions 2 and 4. An interaction, observed for the first time, involves a hydrogen atom and a chlorine atom from opposite sides of the same aromatic ring to give C-H⋯-π(Ar)⋯Cl-C. The parameters are H⋯ring-centroid 2.63 A, Cl⋯ring centroid 3.41 Å, H⋯ring-centroid⋯Cl 167°, C-H⋯ring centroid 159°, C-Cl⋯ring centroid 150.2°. The π(Ar) system is that of the unfused aromatic ring. A second π(Ar) ⋯ Cl-C interaction occurs but this time with the π(Ar) system of the fused aromatic ring. The Cl⋯Cl and Cl⋯O(=C) interactions form the familiar zig-zag pattern which has been noted for many chloroaromatic compounds.

C−Cl...π(Ar)...Cl−C, Cl...Cl and other interactions in the structures of two 6-substituted-2,4-bis(trichloromethyl)-1,3-benzdioxin's: (I) 6-carboxymethyl; (II) 6-propionyl, an antimethanogenesis food additive

AbstractC12H3Cl6O4, (I),Mr=428.91, triclinic,

C−H...π(Ar)...H−C host-guest interactions in a novel air-stable cyanoborate clathrate

P\bar 1

Structure of ethanoldiphenylthallium(III) dithizonate

,a=9.197(1),b=9.336(2),c=9.830(1) Å, α=79.29(1), β=83.33(1), γ=85.38(1)°,V=822.16,Z=2,Dx=1.73 Mg m−3,F(000)=428, λ(MoKα)=0.71069 Å, μ=10.62 cm−1, room temperature, finalR=0.033 for 2573 unique counter reflections withFo>4σ(Fo). C13H10Cl6O3, (II),Mr=426.94, triclinic,