Thomas A. Hamor

Synthesis and Crystal Structure of Undecacarbonyl (triphenylphospine)-triangulo-triruthenium, Ru3(CO)11Ph3P

Abstract Irradiation of Ru 3 (CO) 12 hexane in the presence of triphenylphosphine gives undecacarbonyl (triphenylphosphine)- triangulo -triruthenium in addition to the previously obtained Ru(CO) 4 PPh 3 and Ru(CO) 3 (PPh 3 ) 2 . X-Ray structure determination of the cluster compound reveals a single isomer in which there is a triangle of ruthenium atoms with the triphenylphosphine equatorially substituted and all the carbonyl groups terminally sited. The Ru-Ru distances are 2.907(3), 2.876(3) and 2.875(3)A, with the longest distance cis to the triphenylphosphine ligand. The crystals are monoclinic space group C2/c with a 22.30(2)A, b 16.34(1)A, c 17.42(1)A, B  103.84(4)° and Z  8. The structure was refined to R 7.2% for 1773 observed counter amplitudes.

Tellurated azobenzenes: The crystal and molecular structure of (2-phenylazophenyl-C,7N′)tellurium(IV) trichloride

Abstract The preparation of the title compound via a trans -metallation route has been reinvestigated, and also its formation by direct telluration of azobenzene at 135–150°C has been demonstrated. 13 C NMR data for tellurated and mercurated azobenzene are compared. Reduction with excess hydrazine affords the new ditelluride (C 12 H 9 N 2 ) 2 Te 2 . The crystal structure of (2-phenylazophenyl- C , N ′)tellurium(IV) trichloride has been determined. The coordination about Te is octahedral with a vacant equatorial position, two Cl atoms apical, the third Cl atom and the bidentate organic ligand equatorial. The title compound is essentially monomeric, there are no significant interactions between Te and Cl in neighbouring molecules.

Bis(2-(2-pyridyl)phenyl)tritelluride - synthesis and crystal structure

Abstract The synthesis and molecular structure of bis(2-(2-pyridyl)phenyl)tritelluride are described. There is a short Te⋯N non-bonded interaction of 2.554(7) A, which may be responsible for the stability of the molecule. The tritelluride can be converted into the related ditelluride by treatment with copper in refluxing dioxane. The ditelluride may also be prepared by a route not involving the tritelluride.

Layered ternary transition metal nitrides; synthesis, structure and physical properties

Abstract Two-dimensional structures are an emerging class of materials within nitride chemistry. We report here our systematic studies of two groups of these layered compounds: 1 Lithium transition metal compounds, Li3−x−y□yMxN (M=Co, Ni, Cu, □=Li vacancy) and 2 ternary transition metal nitrides of general formulation AMN2 (A=alkaline earth metal, M=Ti, Zr, Hf). Compounds in class 1 are based on the hexagonal Li3N structure, unique to nitrides. Compounds in group 2, by contrast, crystallise with oxide structures (α-NaFeO2 or KCoO2). Specific and unusual synthetic methods have been developed to reproducibly prepare these compounds. Compounds in series 1 contain ordered or disordered Li vacancies at increased levels relative to the parent Li3N, itself a Li+ fast ion conductor. Nitrides in series 2 should be nominally diamagnetic (S=0), yet magnetic measurements reveal behaviour seemingly inconsistent with this assumption.

The crystal structures of 2-(2′-pyridyl)phenyltellurium(II) bromide and of the inclusion compound bis[2-(2′-pyridyl)phenyltellurium(II) chloride]·p-ethoxyphenyl-mercury(II) chloride

Abstract In 2-(2′-pyridyl)phenyltellurium(II) bromide (1) the coordination about tellurium may be described as pseudo-trigonal bipyramidal wth bromine (TeBr = 2.707(11) A) and nitrogen (TeN) = 2.236(11) A) atoms occupying axial positions. The equatorial plane comprises a carbon atome (TeC = 2.111(6) A) and two lone pairs of electrons. There are no significant intermolecular interactions between the six independent molecules in the unit cell. Bis[2-2′-pyridyl)phenyltellurium(II) chloride]·p-ethoxy-phenylmercury(II) chloride (2) may be regarded as an “inclusion compound” obtained by replacement of two RTeX (X = Cl or Br) molecules by two p-ethoxyphenylmercury(II) chloride entities. There is approximately linear coordination about mercury (CHgCl = 179.2°(4), Hg-C = 2.044(14) and HgCl = 2.328(4) A) and 2-(2′-pyridyl)phenyltellurium(II) chloride, with a structure similar to that of (1) above (TeN = 2.2366(6), TeCl = 2.558(1), TeC = 2.080(25) A). There are no significant intermolecular contacts.

Structure of orthorhombic triphenylphosphine oxide: a redetermination at room temperature

C 18 H 15 OP, M r =278.3, orthorhombic, Pbca, a=29.085 (15), b=9.149 (4), c=11.266 (5) A, V=2997.9 A 3 , Z=8, D x =1.233 g cm -3 , λ(Mo Kα)=0.71069 A, μ=1.170 cm -3 , F(000)=1168, T=295 K, R=0.048 for 1156 observed reflections. The P-O and three P-C bond lengths are 1.487 (3), and 1.795 (5), 1.799 (5) and 1.804 (5) A, respectively. The valence angles at P fall into two categories: the three O-P-C angles, 111.8 (2), 112.0 (2) and 113. 3 (2) o , and the three C-P-C angles, each significantly smaller at 106.4 (2) o

The crystal structure of 1, 1′-(1, 4, 10, 13-tetraoxa-7, 16-diazacyclo-octadecane-7, 16-diyldicarbonyl)ferrocene dihydrate

Abstract The crystal and molecular structure of 1, 1′-(1, 4, 10, 13-tetraoxa-7, 16-diazacyclo-octadecane-7, 16-diyldicarbonyl)ferrocene have been determined. The crystal system is monoclinic, a 8.761(17), b 21.326(18), c 13.250(8)A˚, β 95.56(10)° and space group P21/n. There are two molecules of water for each molecule of the title compound situated outside the cryptand ring system.

Some hydridotris(3,5-dimethylpyrazolyl)borate complexes of zinc, cadmium and mercury—synthetic, structural and NMR investigations

Abstract Attempts to prepare 1 : 1 complexes, L*CdX, where L* = hydridotris(3,5-dimethylpyrazoyl)borate and X = Cl, I, met with limited success. Thus, with X = Cl, CdL*2 was a usual product, although the reactions were not always clean. An L*CdI compound was prepared. By contrast, reactions of KL* with HgCl2 gave L*HgCl cleanly. The reactions of [(Ph3P)2CdCl2] or [(di-2-pyridylamine)CdCl2] with KL* gave “L*Cd(OH) · H2O” in alcoholic media, whereas [(1,2-phenylenediamine)CdI2] on reaction with KL* in Ch2Cl2 gave CdL*2. KL* removed 18-crown-6 from [(18-crown-6(CdCl2] as [(18-crown-6)K]L*. PhHgCl reacted with KL* in THF to give a product of stoichiometry “PhHgL* · 0.5 KCl”. Variable-temperature 1H and 199Hg NMR studies in CDCl3 gave data consistent with the equilibrim with low temperatures favouring the covalent form. Other NMR data are presented and discussed. The crystal structure of CdL*2 is reported, but severe disorder, with the molecule taking up two orientations about a 3 axis, reduced the accuracy of the structure determination. The environment around cadmium is essentially octahedral with a slight trigonal distortion in one molecule (A), but not in the other (B). The CdN distances [2.36(1) in A, 2.43(2) A in B] are in good agreement with those found in analogous cadmium complexes.

THE MAGNETIC AND SECOND-ORDER NONLINEAR OPTICAL PROPERTIES OF SOME PARAMAGNETIC SALTS CONTAINING METALLOCARBABORANE ANIONS

Abstract A series of air-stable salts containing the paramagnetic metallocarboranes [MCb2]− (M = Fe, Ni; Cb2− = 7,8-C2B9H112−) has been prepared and their magnetic properties investigated. The paramagnetic salts [FeIIITp2][FeIIICb2] Tp = HB(C3H3N2)3, [FeIIIC6H4(O)C(Me) = N(CH2)2NHCH22][FeIIICb2], [C5H5NMe][FeIIICb2], [4-MeC5H4NMe][FeIIICb2], [4-PhC5H4NMe][FeIIICb2], [C9H7NMe][FeIIICb2], [FeIIITp2][TCNQ] and [FeIIICp2][FeIIICb2] have been isolated. Magnetic susceptibility measurements show that these salts exhibit typical paramagnetic behaviour with no evidence of cooperative magnetic interactions over the temperature range 6–300 K. The salts [E-Fc-CH = CH-p-C5H4NMe][MIIICb2] (M = Fe, Ni, Co) were also synthesised and their second-order nonlinear optical properties assessed using the Kurtz powder test. Only the cobalt-containing complex gave detectable, though weak, second harmonic generation of 0.01 times urea at 1.907 μm. The salt [C5H5NMe][FeIIICb2] exhibits SHG with an efficiency of 0.5 times urea at 1.907 μm and 0.1 at 1.064 μm. Mass spectrometric and 13C1H NMR studies of the products formed by the degradation of [Co(Cb)2]− by base in the presence of Co2+ ions has provided no evidence for the formation of higher oligomers than the previously reported [Co(Cb)2(C2B8H10)]2− and [CoCb(C2B8H10)2Co]3−. The structures of [FeIIICp2*][NiIIICb2] (Cp* = η5-C5Me5) and [4-MeC5H4NMe][FeIIICb2] have been determined by single crystal X-ray diffraction studies.

Some substitution reactions of ligands coordinated to the bis(cyclopentadienyl)titanium moiety, the X-ray crystal structure of Ti(η5-C5H5)2(OPh)2 and an assessment of the anti-tumour activity of some cyclopentadienyl titanium compounds

Abstract The new complexes Ti(η5-C5H5)Cl(OC6H4NH2-3)2, Ti(η5-C5H5)Cl(O2CPh)2, Ti(η5-C5H5)2(O2C(S)C6H4-1,2), Ti(η5-C5H5)2Cl(SC6H4OH-4), Ti(η5-C5H5)2(OC6H4NH2-3)2 and Ti(η5-C5H5)2Cl(OC6H4Z) (Z = NO2-2, NO2-3, NO2-4, NH2-3) have been synthesized. The free amine group in Ti(η5-C5H5)2Cl(OC6H4NH2-3) reacts with RCl [R = MeCO, PhCO, (OCCO)1/2, Br(CH2)3CO] in the presence of base to give Ti(η5-C5H5)2Cl(R) but, in the absence of base, PhCOCl reacts to give PhCONHC6H4OH-3 and Ti(η5-C5H5)2Cl2. The X-ray crystal structure of Ti(η5-C5H5)2(OPh)2 has been determined and reveals a pseudo-tetrahedral arrangement of the two η5-cyclopentadienyl and two phenoxide ligands around titanium. The Ti—O(Ph) distances are 1.907(3) A and O—Ti—O is 98.1(2)°. The anti-tumour activities of Ti(η5-C5H5)Cl(OC6H4NH2-3)2, Ti(η5-C5H5)Cl(O2CPh)2 and Ti(η5-C5H5)2(O2C(S)C6H4-1,2) have been assessed in vitro using a panel of seven human tumour cell lines.