(Fluoroalkyl)phosphine complexes of nickel(0) and cobalt(I)

The synthesis of a series of (fluoroalkyl)phosphine complexes of nickel is reported. Treatment of (cod)₂Ni with dfepe (dfepe=(C₂F₅)₂PCH₂CH₂P(C₂F₅)₂) yields (dfepe)Ni(cod) (1), which has been structurally characterized. Treatment of 1 with CO or bipy results in the formation of (dfepe)Ni(CO)₂ (2) and (dfepe)Ni(bipy) (3), respectively. Addition of excess dfepe to 1 results in incomplete cod displacement to form (dfepe)₂Ni (4). The homoleptic complex 4 may be independently prepared in high yield by reduction of (acac)₂Ni with (ⁱBu)₃Al in the presence of butadiene and excess dfepe. Solvation of (dfepe)Ni(cod) in acetonitrile gives a new complex tentatively identified as (dfepe)Ni(MeCN)₂ (6), whereas dissolution of (dfepe)₂Ni in acetonitrile leads to a mixture of 6 and the partial displacement product (dfepe)(η¹-dfepe)Ni(MeCN) (5). In contrast to (R₃P)₄Ni(0) phosphine and phosphite complexes, which undergo protonation by strong anhydrous acids such as HCl, H₂SO₄ and CF₃CO₂H to give (R₃P)₄Ni(H)⁺ products, Treatment of (dfepe)₂Ni with neat CF₃CO₂H or excess HOTf in dichloromethane gave no spectroscopic evidence for (dfepe)₂Ni(H)⁺. Exposure for extended periods leads to dfepe loss and decomposition to Ni(II) products. The synthesis of the first cobalt complex of dfepe, (dfepe)Co(CO)₂H, is also reported.     

Bis(hinokitiolato)copper(II): modification (III)

Bis(hinokitiolato)copper(II), Cu(hino)₂, exhibits both antibacterial and antiviral properties, and has been previously shown to exist in two modifications. A third modification has now been confirmed, namely tetrakis(μ₂‐3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olato)bis(3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olato)tricopper(II)–bis(μ₂‐3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olato)bis[(3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olato)copper(II)] (1/1), [Cu(C₁₀H₁₁O₂)₂]₃·[Cu(C₁₀H₁₁O₂)₂]₂, where 3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olate is the systematic name for the hinokitiolate anion. This new modification is composed of discrete [cis‐Cu(hino)₂]₂[trans‐Cu(hino)₂] trimers and [cis‐Cu(hino)₂]₂ dimers. The Cu atoms are bridged by μ₂‐O atoms from the hinokitiolate ligands to give distorted square‐pyramidal and distorted octahedral Cu^II coordination environments. Hence, the Cu^II environments are CuO₅/CuO₆/CuO₅ for the trimer and CuO₅/CuO₅ for the dimer. Each trimer and dimer has crystallographically imposed inversion symmetry. The trimer has never been observed before, the dimer has been seen only once before, and the combination of the two together in the same lattice is unprecedented. The CuO₅ cores exhibit four strong basal Cu—O bonds [1.915 (2)–1.931 (2) Å] and one weak apical Cu—O bond [2.652 (2)–2.658 (2) Å]. The CuO₆ core exhibits four strong equatorial Cu—O bonds [1.922 (2)–1.929 (2) Å] and two very weak axial Cu—O bonds [2.911 (3) Å]. The bite angles for the chelating hinokitiolate ligands range from 83.13 (11) to 83.90 (10)°.     

Ni(II), Pd(II), Cu(II) And Zn(II) complexes with N-(2-Pyridyl)Carbonylaniline (L), Syntheses and X-Ray Crystal structures of [Cu(L)2(H2O)2](No3)2, [Cu(L)2(H2O)2](Clo4)2 and [Zn(L)2(H2O)2](Clo4)2

Reaction of the N-(2-pyridyl)carbonylaniline ligand (L) with Cu(NO₃)₂, Cu(ClO₄)₂, Zn(ClO₄)₂, Ni(NO₃)₂ and PdCl₂ gives complexes with stoichiometry [Cu(L)₂(H₂O)₂](NO₃)₂, [Cu(L)₂(H₂O)₂](ClO₄)₂, [Zn(L)₂(H₂O)₂] (ClO₄)_2, [Ni(L)₂(H₂O)Cl](NO₃) and PdLCl₂. The new complexes were characterized by elemental analyses and infrared spectra. The crystal structures of [Cu(L)₂(H₂O)₂](NO₃)₂, [Cu(L)₂(H₂O)₂](ClO₄)₂, and [Zn(L)₂(H₂O)₂](ClO₄)₂ were determined by X-ray crystallography. The cation complexes [M(L)₂(H₂O)₂] contain copper(II) and zinc(II) with distorted octahedral geometry with two N-(2-pyridyl)carbonylaniline (L) ligands occupying the equatorial sites. The hexa-coordinated metal atoms are bonded to two pyridinic nitrogens, two carbonyl oxygens and two water molecules occupying the axial sites. Both the coordinated water molecules and uncoordinated amide NH groups of the N-(2-pyridyl)carbonylaniline (L) ligands are involved in hydrogen bonding, resulting in infinite hydrogen-bonded chains running in one and two-dimensions.     

Tin(II) aminoalkoxides and heterobimetallic derivatives: the structures of Sn6(O)4(dmae)4, Sn6(O)4(OEt)4 and [Sn(dmae)2Cd(acac)2]2

Tin(II) methoxide reacts with N,N′‐dimethylaminoethanol (dmaeH) to yield Sn(dmae)₂ ( 1 ) along with small amounts of the hydrolysis product Sn₆(O)₄(dmae)₄ ( 2 ). The geometrically more regular iso‐structural cage Sn₆(O)₄(OEt)₄ ( 3 ) was obtained as the only tractable product isolated from reaction of 2 and Sb(OEt)₃, while 1 reacted with CdX₂ (X = acac, I) to afford Sn(dmae)₂Cd(acac)₂ ( 4 ) and Sn(dmae)₂CdI₂ ( 5 ). The X‐ray structures of 2, 3 and 4 are reported. Decomposition of 4 under aerosol‐assisted chemical vapour deposition conditions leads to amorphous tin oxide films with no detectable cadmium (i.e. ca < 2% cadmium), rather than a stoichiometric Sn:Cd oxide. Copyright © 2006 John Wiley & Sons, Ltd.     

Hexaaquacobalt(II) bis(hypophosphite) and hexaaquacobalt(II)/nickel(II) bis(hypophosphite)

The title compounds, hexa­aqua­cobalt(II) bis­(hypophosphite), [Co(H₂O)₆](H₂­PO₂)₂, and hexa­aqua­cobalt(II)/nickel(II) bis(hypophosphite), [Co_0.5Ni_0.5(H₂O)₆](H₂PO₂)₂, are shown to adopt the same structure as hexa­aqua­magnesium(II) bis­(hypophosphite). The packing of the Co(Ni) and P atoms is the same as in the structure of CaF₂. The Co^II(Ni^II) atoms have a pseudo‐face‐centred cubic cell, with a = b～ 10.3 Å, and the P atoms occupy the tetrahedral cavities. The central metal cation has a slightly distorted octahedral coordination sphere. The geometry of the hypophosphite anion in the structure is very close to ideal, with point symmetry mm2. Each O atom of the hypophosphite anion is hydrogen bonded to three water mol­ecules from different cation complexes, and each H atom of the hypophosphite anion is surrounded by three water mol­ecules from further different cation complexes.     

(Chloromethyl)thallium(III) compounds

Aryl(chloromethyl)thallium chlorides, Ar(ClCH₂)TlCl (Ar=C₆H₅, p-CH₃C₆H₄) have been prepared by treatment of arylthallium dichlorides with diazomethane. The derived carboxylates, Ar(ClCH₂)TlX, react with HgX₂ to give the dicarboxylates, (ClCH₂)TlX₂ (X = OCOCH₃, OCOC₃H₇-i) and with tetramethyltin to give CH₃(ClCH₂)TlX compounds. R(ClCH₂)TIX compounds (R = CH₃, C₆H₅, p-CH₃C₆H₄) undergo disproportionation in methanol to R₂TlX and (ClCH₂)₂TlX compounds.     

Synthese und Struktur der Platin(O)-Verbindungen [(dipb)Pt]2(COD) und (dipb)3Pt2 sowie des clusters Hg6[Pt(dipb)]4 (dipb = (i-Pr)2P(CH2)4P(i-Pr)2)

Synthesis and Structure of the Platinum(0) Compounds [(dipb)Pt]₂(COD) and (dipb)₃Pt₂ and of the Cluster Hg₆[Pt(dipb)]₄ (dipb = (i-Pr)₂P(CH₂)₄P(i-Pr)₂) The reduction of (dipb)PtCl₂ with Na/Hg yields (dipb)Pt as an intermediate which reacts with the amalgam to form the cluster Hg₆[Pt(dipb)]₄ ( 3 ) or decomposes to (dipb)₃Pt₂ ( 2 ) and Pt. In the presence of COD [(dipb)Pt]₂(COD) ( 1 ) is obtained. 1 crystallizes monoclinicly in the space group P2₁/c with a = 1596.1(4), b = 996.5(2), c = 1550.4(3) pm, β = 113.65(2)°, Z = 2. In the dinuclear complex two (dipb)Pt units are bridged by a 1,2-η²-5,6-η² bonded COD ligand. Whereby the C = C double bonds are lengthened to 145 pm. 2 forms triclinic crystals with the space group P1 and a = 1002.0(2), b = 1635.9(3), c = 868.2(2) pm, α = 94.70(2)°, β = 94.45(2)°, σ = 87.95(1)°, Z = 1. In 2 two (dipb)Pt moieties are connected by a μ-dipb ligand in a centrosymmetrical arrangement. 3 is monoclinic with the space group C2/c and a = 1273.8(3), b = 4869.2(6), c = 1660.2(3) pm, β = 95.16(2)°, Z = 4. The clusters Hg₆[Pt(dipb)]₄ have the symmetry C₂. Central unit is a Hg₆ octahedron of which four faces are occupied by Pt(dipb) groups. The bonding in the cluster is discussed on the basis of eight Pt? Hg two center bonds of 267.6 pm and two Pt? Hg? Pt three center bonds with Pt? Hg = 288.0 pm.     

Die Kristallstruktur von p-Tolylbis(diethyldithiocarbamato)-thallium(III) und Phenylbis(methylxanthogenato)bismut(III)

Crystal Structure of p-Tolylbis (diethyldithiocarbamato)thallium(III) and Phenylbis-(methylxanthogenato)bismut(III) The crystal structure of 4-CH₃(C₆H₄)? Tl(S₂CN(C₂H₅)₂)₂ (P2₁/c, a = 11.973(3), b = 10.692(3), c = 19.232(4) Å, β = 114.02(2)°, Z = 4) and C₆H₅-Bi(S₂COCH₃)₂ (P2₁/c, a = 6.395(2), b = 24.684(8), c = 9.732(3) Å, β = 101.38(3)°, Z = 4) was solved from X-ray diffraction data of single crystals. From the interatomic distances follows that the dithiocarbamate and xanthogenate ligands coordinate asymmetrically bidentate to the metal as presumed and exclusively through the sulfur atoms. Differences in the coordination sphere of bismut and thallium give evidence for a “stereochemically active lone pair” on the bismut atom.     

Synthese und Strukturbestimmung von (i-Pr)2NB(t-BuP)3 und (i-Pr)2NB(t-BuP)4

Synthesis and Structure Analysis of (i-Pr)₂NB(t-BuP)₃ and (i-Pr)₂NB(t-BuP)₄ The diphosphide K(t-Bu)P-(t-BuP)₂-P(t-Bu)K obtained by the cleavage reaction of the 3-membered ring system (i-Pr)₂BN(t-BuP)₂ with potassium reacts with t-BuPCl₂ at ?78°C under ring expansion to form the P₃B ring system (i-Pr)₂NB(t-BuP)₃ – 1,2,3-tri-t-butyl-tri-phospha-4-diisopropyl-aminoboretane ( 1 ). – The 5-membered P₄B ring system (i-Pr)₂NB(t-BuP)₄ – 1,2,3,4-tetra-t-butyl-tetraphospha-5-diisopropylaminoborolidine, ( 2 ) – is formed from K(t-Bu)P? (t-BuP)₂? P(t-Bu)K and (i-Pr)₂NBCl₂ analogous to the above reaction. 1 and 2 could be obtained in a pure form and characterized NMR spectroscopically and by X-ray structure analysis. 1 shows at 200 K two conformation isomers; for 2 ³¹P-^10,11B-isotopic shifts could be identified.     

Crystal structures of bis(diethylenetriamine)cobalt(III) Heptachlorodimercurate(II)mer-[Co(Dien)2]Hg2Cl7 and (diethylenetriamine)glycylglycinato(1-) cobalt(III) hexachlorodimercurate(II) [Co(Dien)HGlygly]Hg2Cl6

An X-ray diffraction analysis was performed for crystalline [Co(Dien)₂]Hg₂Cl₇ (a = 14.452(2), b = 9.831(1), c = 15.967(2) åΒ = 97.17(1)?, space group P2₁/c, Z = 4) and [Co(Dien)HGlygly]Hg₂Cl₆ (a = 7.693(1), b = 14.439(2), c = 19.961(2) å, Β = 100.31(1)?, space group P2₁ Z = 2), where Dien is diethylenetriamine and HGlygly is the glycylglycine anion [H₂NCH₂C(OH) = NCH₂CO₂]. The anionic moiety is represented by isolated centrosymmetric ions [Hg₄Cl₁₄]_6- in the former and by infinite chains [Hg₂Cl₆] _n ^2n- in the latter (the chain is composed of two alternating vertex-sharing nonequivalent tetrahedral groups HgCl₄. In the cobalt(III) complex cations, the extreme donating atoms of the Dien and HGlygly ligands are in the trans positions of the coordination octahedron.     

Synthesis and reactions of phenylimidotrimethyl-bis(trimethylphosphine)-rhenium(V). Synthesis and X-ray crystal structure of bis(trimethylsilylmethyl)oxo-rhenium(V)-μ-oxo-tetrakis(trimethylphosphine)rhenium (I)-(trimethylsilylmethyl)dioxorhenium(V), (ReRe)

The interaction of phenylimidotrichloro bis(trimethylphosphine) with dimethylmagnesium gives the trimethyl compound, Re(NPh)Me₃(PMe₃)₂. Exchange reactions between the trichloro and trimethyl compounds are studied by ¹H nuclear magnetic resonance and the intermediates Re(NPh)Me₂Cl(PMe₃)₂ and Re(NPh)MeCl₂(PMe₃)₂ isolated.The trimethyl reacts with fluoroboric acid to give a phenylamido complex [Re(NHPh)Me₂F(PMe₃)₂]BF₄, with acetic acid to give Re(NPh)Me(CO₂Me₃)₂, and with trityltetrafluoroborate to give [Re(NPh)Me₂(PMe₃)₂]BF₄.The interaction of Re(NPh)Cl₃(PMe₃)₂ with excess of bis(trimethylsilylmethyl)magnesium and of trimethyl-phosphine in tetrahydrofuran gives an unusual tri-rhenium compound, (Me₃SiCH₂)₃(O)Re-μ-O-Re(PMe₃)₄Re(O)₂(CH₂SiMe₃) whose structure as a thf solvate, has been determined by X-ray crystallography. Crystals of the latter are monoclinic, space group P2₁/n with a = 15.512(3), b = 15.392(2), c = 21.506(4) Å, β = 100.19(2)°, Z = 4. The structure has been refined to an R of 0.07 for 5028 observed diffractometer data. The molecule is tri-nuclear with the central rhenium carrying four PMe₃ groups being bound to the second rhenium by a short ReRe bond and to the third by an asymmetric oxygen bridge. The end rhenium bound to the bridge oxygen carries two CH₂SiMe₃ groups and an oxygen atom, while the other has one CH₂SiMe₃ group and two oxygen atoms.     

Mixed ligand titanium(IV) complexes. Chlorobis(dithiocarbamato)bis(methylsalicylato)titanium(IV) andbis(dithiocarbamato)bis(methylsalicylato)titanium(IV)

Summary Dichlorobis(methylsalicylato)titanium(IV) reacts with potassium or amine salts of dialkyl or diaryl dithiocarbamates in 11 and 12 molar ratios in anhydrous benzene (room temperature) or in boiling CH₂Cl₂ to yield mixed ligand complexes: (AcOC₆H₄O)₂ Ti(S₂CNR₂)Cl (1) and (AcOC₆H₄O)₂ Ti(S₂CNR₂)₂ (2), R=Et, n-Pr, n-Bu, cyclo-C₄H₈ and cyclo-C₅H₁₀. These compounds are moisture sensitive and highly soluble in polar solvents. Molecular weight measurement in conjunction with i.r.,¹H and¹³C n.m.r. spectral studies suggest coordination number 7 and 8 around titanium(IV) in (1) and (2) respectively.     

Studies on Mn(II) and Mn(IV) Complexes of an Unsymmetrical Bidentate Donor,N(4-Chlorophenyl)-Pyridine-2-Aldimine (ClL): Crystal Structure of [Mn(ClL)2(NCS)2]

The synthesis, characterisation and X-ray structure of an Mn(II) compound, [Mn(ClL)₂(NCS)₂], is described. Oxidation of the compound by H₂O₂ leads to a mononuclear Mn(IV) compound [Mn(ClL)(ClL')(NCS)₂]ClO₄·2H₂O where one of the ClL ligands is oxidised to the corresponding amide ClL'. Oxidation of [Mn(ClL)₂(NCS)₂] by Ce(IV), however, leads to a binuclear Mn(IV) compound [Mn₂O(ClL')₃(ClL)(H₂O)₂](NCS)₂ClO₄·2MeCN. Electron transfer behaviour of the compounds was investigated by cyclic voltammetry and differential pulse voltammetry.     

SYNTHESIS AND STRUCTURES OF DICHLOROTETRAKIS-(PHENYLTHIOUREA) CADMIUM(II) AND CATENA-BIS(THIOCYANATE) BIS(PHENYLTHIOUREA)CADMIUM(II)

Abstract

Two new cadmium(II) complexes with phenylthiourea (PTU), namely Cd(PTU)₄Cl₂ (1) and [Cd₂(NCS)₂(μ₂-SCN)₂(PTU)₂(μ₂-PTU)₂] _n (2), have been prepared and characterized structurally by X-ray diffaction. Complex 1 crystallizes in the monoclinic space group C2/c, with a = 27.057(13), b = 8.108(3), c = 16.751(8) Å, β = 114.46°, V = 3345(3) ų, Z = 4. Complex 2 crystallizes in the triclinic space group P-1, with a = 9.336(3), b = 14.686(5), c = 16.911(5) Å, α = 71.36(2), β = 84.31(2), γ = 72.470(10)°, V = 2095.0(12) ų Z = 4. The structural analysis shows that each metal atom in both the mononuclear complex 1 and polynuclear complex 2 is octahedrally coordinated by four sulfur atoms and two chloro ligands or two nitrogen atoms from the thiocyanate groups, respectively. The PTU ligand can serve as either a monodentate ligand or a μ₂-bridging ligand upon coordination to a metal atom.     

Synthesis and reactions of trans-dicarbonyl bis-[1,2-bis(dimethylphosphino)ethane] vanadium(O): X-ray crystal structures of trans-V(CO)2(dmpe)2 [cis-V(CO)2(dmpe)2(CH3CN)]BPh4 and cis-V(CO)2(dmpe)2(O2CEt)

Interaction of trans-VCl₂(dmpe)₂ with sodium amalgam in tetrahydrofuran under CO gives trans-V(CO)₂(dmpe)₂. The latter is oxidized by Ag⁺ in acetonitrile to give [cis-V(CO)₂(dmpe)₂(CH₃CN)]⁺, isolated as the tetraphenylborate. Interactions with acids (HX) gives neutral complexes of the type V(CO)₂(dmpe)₂X (X = Cl, MeCO₂, EtCO₂, CF₃CO₂, PhPO₂H or NH₂SO₃); the chloride can be exchanged with N₃⁻ or CN⁻ in methanol. X-ray structural studies confirm the trans stereochemistry for V(CO)₂(dmpe)₂ and the seven-coordination of V^I in both [V(CO)₂(dmpe)₂(CH₃CN)][BPh₄] and V(CO)₂(dmpe)₂(O₂CEt), which have a pseudo octahedral geometry with the two carbonyls occupying a “split” axial site. ⁵¹V NMR and other spectra are reported.     

Synthese und Strukturen neuer selenido‐ und selenolatoverbrückter Kupfercluster: [Cu38Se13(SePh)12(dppb)6] (1), [Cu(dppp)2][Cu25Se4(SePh)18(dppp)2] (2), [Cu36Se5(SePh)26(dppa)4] (3), [Cu58Se16(SePh)24(dppa)6] (4) und [Cu3(SeMes)3(dppm)] (5)

Syntheses and Crystal Structures of new Selenido‐ and Selenolato‐bridged Copper Clusters: [Cu₃₈Se₁₃(SePh)₁₂(dppb)₆] (1), [Cu(dppp)₂][Cu₂₅Se₄(SePh)₁₈(dppp)₂] (2), [Cu₃₆Se₅(SePh)₂₆(dppa)₄] (3), [Cu₅₈Se₁₆(SePh)₂₄(dppa)₆] (4), and [Cu₃(SeMes)₃(dppm)] (5) The reactions of copper(I) chloride or copper(I) acetate with monodentate phosphine ligands (PR₃; R = organic group) and Se(SiMe₃)₂ have already lead to the formation of CuSe clusters with up to 146 copper and 73 selenium atoms. If the starting materials and the bidentate phosphine ligands (Ph₂P–(CH₂)_n–PPh₂, n = 1: dppm, n = 3: dppp, n = 4: dppb; Ph₂P–C≡C–PPh₂: dppa) and silylated chalcogen derivates are changed (RSeSiMe₃; R = Ph, Mes) a series of new CuSe clusters can be synthesized. From single crystal X‐ray structure analysis one can characterise [Cu₃₈Se₁₃(SePh)₁₂(dppb)₆] ( 1 ), [Cu(dppp)₂] · [Cu₂₅Se₄(SePh)₁₈(dppp)₂] ( 2 ), [Cu₃₆Se₅(SePh)₂₆(dppa)₄] ( 3 ), [Cu₅₈Se₁₆(SePh)₂₄(dppa)₆] ( 4 ) and [Cu₃(SeMes)₃(dppm)] ( 5 ). In this new class of CuSe clusters, compounds 1 and 4 possess a spherical cluster skeleton, wheras 2 and 3 have a layered cluster core.     

Electrochemical behaviour of dicyanobis(2,2′-bipyridine) ruthenium(II) and dicyanobis(1,10-phenanthroline) ruthenium(II) complexes

The electrochemical behaviour of Ru(bipy)₂(CN)₂ and Ru(phen)₂(CN)₂ (bipy=2,2′-bipyridine; phen=1,10-phenanthroline) has been investigated in dimethylformamide. Both complexes exhibit one oxidation wave and three reduction waves. In the case of Ru(bipy)₂-(CN)₂ the anodic process and the first two cathodic processes involve one electron and are reversible in the time scale of polarographic and cyclic voltammetric experiments. The third reduction step is irreversible and has been attributed to the addition of three electrons to Ru(bipy)₂(CN)₂ followed by liberation of one or more ligands and reduction of liberated bipyridine. The features of the redox processes for the Ru(phen)₂(CN)₂ are similar to those found for the bipy complex except for the first reduction wave, which is complicated by adsorption phenomena. A qualitative MO discussion of the redox processes is also reported.     

New biimidazole and bibenzimidazole derivatives: mono and binuclear palladium(II) or platinum(II) complexes and heterobinuclear palladium(II)-rhodium(I) or platinum(II)-rhodium(I) complexes

Novel neutral biimidazolate or bibenzimidazolate palladium(II) and platinum(II) complexes of the type M(NN)₂(dpe) [M = Pd, Pt; (NN)₂^2? = BiIm^2?, BiBzIm^2?. dpe = 1,2-bis(diphenylphosphino) ethane] have been obtained by reacting MCl₂(dpe) with TI₂(NN)₂. Complexes M(NN)₂(dpe) which are Lewis bases react with HClO₄ or [M(dpe)(Me₂CO)₂](ClO₄)₂ to yield, respectively, mononuclear cationic complexes of general formula [M{H₂(NN)₂](dpe) (M = Pd, Pt; H₂(NN)₂ = H₂BiIm, H₂BiBzIm) and homobinuclear palladium(II) or platinum(II) cationic complexes of the type [M₂{μ - (NN)₂}(dpe)₂](ClO₄)₂. Reactions of M(BiBzIm)(dpe) with [Rh(COD) (Me₂CO)_X](ClO₄) render similar heterobinuclear palladium(II)-rhodium(I) and platinum(II)-rhodium(I) cationic complexes, of general formula [(dpe)M(μ-BiBzIm)Rh(COD)](ClO₄) (M = Pd, Pt; COD = 1,5-cyclooctadiene). Di- and mono-carbonyl derivatives [(dpe)M(μ-BiBzIm)Rh(CO)L](ClO₄) (M = Pd, Pt; L = CO, PPh₃) have also been prepared. The structures of the resulting complexes have been elucidated by conductance studies and IR spectroscopy.     

Thallium(I)-Uranates(VI)

The solid state preparation, thermal and hydrolytic characteristics of thallium(I)—uranates(VI) are described. The phases identified were Tl₂UO₄, Tl₂U₂O₇ and a range of solid solution (Tl₂O. 2,33 UO₃? Tl₂O. 6 UO₃). The thallium uranates are isostructural with the corresponding potassium uranates. Tl₂U₂O₇ is the stable phase formed from the other uranates on hydrolytic treatment. The thallium uranates lose thallium(I) oxide on heating to temperatures above 750°C and the order of thermal stability is Tl₂U₆O₁₉～Tl₂U₃O₁₀～Tl₂U₂O₇»Tl₂UO₄.     

Dihalodicarbonylruthenium(II)-bis(tertiaryphosphine chalcogenide) complexes

Summary Reactions of 1,1-methylene bis(diphenylphosphine oxide or sulphide) (dpmO₂ or dpmS₂) and 1-(diphenylphosphinoethyl)-2-diphenylphosphine sulphide (dpePS) with dihalodicarbonylruthenium(II) in EtOH gave 1:1 (L:M) complexes of stoichiometry: Ru(CO)₂X₂L₂ (L = dpmO₂, dpmS₂ or dpePS; X = Cl or Br), which were characterized by elemental analysis and i.r. spectroscopy. The spectra reveal that: (a) the carbonyls occupy octahedral cis-positions, and (b) dpmS₂ shows a higher coordination shift than does dpePS, probably due to the better Lewis basicity of the Ph₂P moiety as compared to the Ph₂P(S) moiety in the ligands. Cis-octahedral geometries are inferred from these studies.