Mono‐ and Bis(pyrrolo)tetrathiafulvalene Derivatives Tethered to C60: Synthesis,Photophysical Studies,and Self‐Assembled Monolayers

A series of mono‐ (MPTTF) and bis(pyrrolo)tetrathiafulvalene (BPTTF) derivatives tethered to one or two C₆₀ moieties was synthesized and characterized. The synthetic strategy for these dumbbell‐shaped compounds was based on a 1,3‐dipolar cycloaddition reaction between aldehyde‐functionalized MPTTF/BPTTF derivatives, two different tailor‐made amino acids, and C₆₀. Electronic communication between the MPTTF/BPTTF units and the C₆₀ moieties was studied by a variety of techniques including cyclic voltammetry and absorption spectroscopy. These solution‐based studies indicated no observable electronic communication between the MPTTF/BPTTF units and the C₆₀ moieties. In addition, femtosecond and nanosecond transient absorption spectroscopy revealed, rather surprisingly, that no charge transfer from the MPTTF/BPTTF units to the C₆₀ moieties takes place on excitation of the fullerene moiety. Finally, it was shown that the MPTTF–C₆₀ and C₆₀–BPTTF‐C₆₀ dyad and triad molecules formed self‐assembled monolayers on a Au(111) surface by anchoring to C₆₀.     

Ground‐State Equilibrium Thermodynamics and Switching Kinetics of Bistable [2]Rotaxanes Switched in Solution,Polymer Gels,and Molecular Electronic Devices

We report on the kinetics and ground‐state thermodynamics associated with electrochemically driven molecular mechanical switching of three bistable [2]rotaxanes in acetonitrile solution, polymer electrolyte gels, and molecular‐switch tunnel junctions (MSTJs). For all rotaxanes a π‐electron‐deficient cyclobis(paraquat‐p‐phenylene) (CBPQT⁴⁺) ring component encircles one of two recognition sites within a dumbbell component. Two rotaxanes (RATTF⁴⁺ and RTTF⁴⁺) contain tetrathiafulvalene (TTF) and 1,5‐dioxynaphthalene (DNP) recognition units, but different hydrophilic stoppers. For these rotaxanes, the CBPQT⁴⁺ ring encircles predominantly (>90 %) the TTF unit at equilibrium, and this equilibrium is relatively temperature independent. In the third rotaxane (RBPTTF⁴⁺), the TTF unit is replaced by a π‐extended analogue (a bispyrrolotetrathiafulvalene (BPTTF) unit), and the CBPQT⁴⁺ ring encircles almost equally both recognition sites at equilibrium. This equilibrium exhibits strong temperature dependence. These thermodynamic differences were rationalized by reference to binding constants obtained by isothermal titration calorimetry for the complexation of model guests by the CBPQT⁴⁺ host in acetonitrile. For all bistable rotaxanes, oxidation of the TTF (BPTTF) unit is accompanied by movement of the CBPQT⁴⁺ ring to the DNP site. Reduction back to TTF⁰ (BPTTF⁰) is followed by relaxation to the equilibrium distribution of translational isomers. The relaxation kinetics are strongly environmentally dependent, yet consistent with a single electromechanical‐switching mechanism in acetonitrile, polymer electrolyte gels, and MSTJs. The ground‐state equilibrium properties of all three bistable [2]rotaxanes were reflective of molecular structure in all environments. These results provide direct evidence for the control by molecular structure of the electronic properties exhibited by the MSTJs.     

Ground-state equilibrium thermodynamics and switching kinetics of bistable [2]rotaxanes switched in solution, polymer gels, and molecular electronic devices

We report on the kinetics and ground-state thermodynamics associated with electrochemically driven molecular mechanical switching of three bistable [2]rotaxanes in acetonitrile solution, polymer electrolyte gels, and molecular-switch tunnel junctions (MSTJs). For all rotaxanes a pi-electron-deficient cyclobis(paraquat-p-phenylene) (CBPQT4+) ring component encircles one of two recognition sites within a dumbbell component. Two rotaxanes (RATTF4+ and RTTF4+) contain tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) recognition units, but different hydrophilic stoppers. For these rotaxanes, the CBPQT4+ ring encircles predominantly (>90 %) the TTF unit at equilibrium, and this equilibrium is relatively temperature independent. In the third rotaxane (RBPTTF4+), the TTF unit is replaced by a pi-extended analogue (a bispyrrolotetrathiafulvalene (BPTTF) unit), and the CBPQT4+ ring encircles almost equally both recognition sites at equilibrium. This equilibrium exhibits strong temperature dependence. These thermodynamic differences were rationalized by reference to binding constants obtained by isothermal titration calorimetry for the complexation of model guests by the CBPQT4+ host in acetonitrile. For all bistable rotaxanes, oxidation of the TTF (BPTTF) unit is accompanied by movement of the CBPQT4+ ring to the DNP site. Reduction back to TTF0 (BPTTF0) is followed by relaxation to the equilibrium distribution of translational isomers. The relaxation kinetics are strongly environmentally dependent, yet consistent with a single electromechanical-switching mechanism in acetonitrile, polymer electrolyte gels, and MSTJs. The ground-state equilibrium properties of all three bistable [2]rotaxanes were reflective of molecular structure in all environments. These results provide direct evidence for the control by molecular structure of the electronic properties exhibited by the MSTJs.     

A BPTTF-based self-assembled electron-donating triangle capable of C60 binding

A kinetically stable self-assembled redox-active triangle is isolated. The resulting electron-donating cavity, which incorporates three BPTTF units, exhibits a remarkable binding ability for electron-deficient C(60), supported by a favorable combination of structural and electronic features.     

Bispyrrolotetrathiafulvalene-containing [2]catenanes

Two [2]catenanes incorporating bispyrrolotetrathiafulvalene (BPTTF) and weaker aryl donors, hydroquinone (HQ) and 1,5-dioxynaphthalene (DNP), respectively, have been prepared and characterized. These [2]catenanes show a predominant amount (>95:5) of the co-conformation in which either the HQ or the DNP unit is encircled by a tetracationic cyclophane, cyclobis(paraquat-p-phenylene) (CBPQT4+), contrary to what is observed in systems based on the parent tetrathiafulvalene (TTF). These new [2]catenanes act effectively as molecular switches which are always configured in the "on" state.     

A metal-directed self-assembled electroactive cage with bis(pyrrolo)tetrathiafulvalene (BPTTF) side walls

A straightforward synthesis of a bis(pyrrolo)tetrathiafulvalene (BPTTF)-based tetratopic ligand bearing four pyridyl units is described. The first example of a TTF-based self-assembled cage has been produced from this redox-active ligand through metal-directed synthesis with a cis-coordinated square-planar Pt(II) complex. The resulting cage corresponds to a trigonal-prismatic structure, as shown by X-ray crystallography. A UV-vis titration indicated that the electron-rich cavity can be used to incorporate one molecule of tetrafluorotetracyano-p-quinodimethane (TCNQF(4)).     

Darstellung von Acetatoblei(IV)- und Acetatozinn(IV)- manganpentacarbonylen durch Acidolyse von (C6H5)4–n−M[Mn(CO)5]n (M  Sn,Pb; n = 1, 2) mit Essigsäure

Preparation of Acetatolead(1V) and Acetatotin(1V) Manganese Pentacarbonyls by Acidolysis of (C₆H₅)_4?n M[Mn(CO)₅]_n (M ? Sn, Pb; n = 1, 2) with Acetic Acid By acidolysis of (C₆H₅)_4?nM[Mn(CO)₅]_n (M ? Sn, Pb; n = 1, 2) with acetic acid no M? Mn bonds are broken, but M? C bonds. In this reaction (CH₃COO)₂M[Mn(CO)₅]₂ is formed from (C₆H₅)₂M[Mn(CO)₅]₂, and (CH₃COO)₃SnMn(CO)₅ and (CH₃COO)₂C₆H₅PbMn(CO)₅ from (C₆H₅)₃MMn-(CO)₅. (CH₃COO)₂C₆H₅SnMn(CO)₅ is prepared from Cl₂C₆H₅SnMn(CO)₅ and AgCH₃COO. According to IR spectroscopic data the acetato ligands of the diacetato complexes are bidentate, while in (CH₃COO)₃SnMn(CO)₅ bi- and monodentate carboxylate groups are present. For the central atoms Sn and Pb octahedral coordination is proposed.     

Darstellung und Eigenschaften von Chromtricarbonyl-Komplexen strukturisomerer Borazin-Derivate

The new hexaalkylborazine chromium tricarbonyls (n-Pr)₃B₃N₃Me₃Cr(CO)₃ (V), Me₃B₃N₃(n-Pr)₃Cr(CO)₃ (VI), (i-Pr)₃B₃N₃Me₃Cr(CO)₃ (VII) and Me₃B₃N₃(i-Pr)₃Cr(CO)₃ (VIII) have been prepared from fac-Cr(CO)₃(MeCN)₃ and the corresponding borazine in dioxane or without solvent. They are much more labile than the isomeric complex Et₃B₃N₃Et₃Cr(CO)₃ (IV) which can be readily obtained from Et₃B₃N₃Me₃Cr(CO)₃ and Et₃B₃N₃Et₃ by ring ligand exchange. The NMR., IR., UV. and Mass spectroscopic data of the complexes IV–VIII will be briefly discussed. The preparation of the borazine derivatives (n-Pr)₃B₃N₃Me₃ (IX) and Me₃B₃N₃(n-Pr)₃ (X) is also reported.     

The acid properties of benzodiamyloxyl and thiadiazole porphyrazine derivatives in the H<Subscript>2</Subscript>L-(K[2.2.2])OH-DMSO system

Step acid dissociation reactions of benzodiamyloxyl (X) and thiadiazole (Y) porphyrazine (H₂PA) derivatives H₂PA(X)₄, H₂PA(X)₃(Y), H₂PA(X)₂(Y)₂, H₂PA(X)(Y)₃, and H₂PA(Y)₄ were studied theoretically (MP3) and experimentally (spectropotentiometrically) in the H₂L-(K[2.2.2])OH-DMSO system for the series H₂P (porphin), H₂P(μs-Pr)₄, H₂P(μs-Ph)₄, H(N-Me)P(μs-Ph)₄, H₂TBP (tetrabenzoporphin), H₂TBP(μs-Ph)₄, H₂PA (porphyrazine), H₂PA(β-Ph)₄, H₂PC (phthalocyanine), and H₂PC(t-Bt)₄. The linear correlation pK _a1 ²⁹⁸ = 0.32622ΔH°_a1(g) ? 94.62 (R = 0.998) was observed for H₂PA and its symmetrical derivatives H₂PA(β-Ph)₄, H₂PC, H₂PC(t-Bt)₄, H₂PC(X)₄, and H₂PC(Y)₄. Deviations of the proportionality factors in the pK _a1 ²⁹⁸ = bH°_a1(g) + A dependences from the theoretical value (2.303RT)^?1 were explained by medium effects. Substituent effects on pK _a1 ²⁹⁸ were divided into internal δ(R _i)_int and external δ(R _i)_ext (solvation) contributions. The compensation dependences δ(R _i)_ext = ?0.10911δ(R _i)_int + 0.13 and δ(R _i)_ext = ?0.52969δ(R _i)_int (correlation coefficients 0.998) were observed for simple (H₂PA, H₂TBP, H₂P(μs-Ph)₄, and H₂P(μs-Pr)₄) and complex (H(N-Me)P(Ph)₄, H₂TBP(μs-Ph)₄, H₂PA(β-Ph)₄,H₂PA(Y)₄, H₂PC, H₂PC(t-Bt)₄, and H₂PC(X)₄) porphin derivatives, respectively.     

The formal umpolung behaviour of protonic acids containing coordinating anions towards diphosphazane-bridged derivatives of nonacarbonyldiruthenium

Reaction of [Ru₂(μ-CO)(CO)₄{μ-(RO)₂PN(Et)(OR)₂}₂] (R = Me or Prⁱ) with the protonic acids HCl, HBr, HNO₃, H₂BO₂F, CF₃COOH, PhSH/HPF₆, and H₂CO₃/HPF₆ produces [Ru₂A(CO)₅ {μ-(RO)₂PN(Et)(OR)₂}₂]⁺ and/or [Ru₂(μ-A)(CO)₄{μ-(RO)₂PN(Et)(OR)₂}₂]⁺ (A = Cl, Br, ON(O)O, OB(F)OH, OC(CF₃)O, SPh, and OC(OH)O) via [Ru₂H(CO)₅{μ-(RO)₂PN(Et)(OR)₂}₂]⁺ as intermediate; the structure of [Ru₂{μ-OB(F)OH}(CO)₄{-(PrⁱO)₂PN(Et)P(OPrⁱ)₂}]⁺ has been established X-ray crystallographically.     

Reactions of 1-(3"-Amino)- and 1-(3"-Acetamido)propylsilatranes with Cobalt(II) Chloride and Dicobalt Octacarbonyl

1-(3"-Amino)propylsilatrane (I) and 1-(3"-acetamido)propylsilatrane (II) react with anhydrous cobalt(II) chloride to give dichlorobis[1-(3"-amino)propylsilatrane]cobalt(II) {Co[NH₂CH₂CH₂CH₂Si(OCH₂CH₂)₃N]₂Cl₂} (III) and dichlorobis[1-(3"-acetamido)propylsilatrane]cobalt(II) {Co[CH₃C(O)NHCH₂CH₂CH₂Si(OCH₂CH₂)₃N]₂Cl₂} (IV). Being unstable, compound IV transforms into an imidic acid derivative. Reactions of silatranes I and II with dicobalt octacarbonyl afford hexakis[1-(3"-aminoamido)propylsilatrane]cobalt(II) bis(tetracarbonylcobaltate) {Co[NH₂CH₂CH₂CH₂Si(OCH₂CH₂)₃N]_4.8[HC(O)NHCH₂CH₂CH₂Si(OCH₂CH₂)₃N]_1.2}[Co(CO)₄]₂ (V) and hexakis[1-(3"-acetamido)propylsilatrane]cobalt(II) bis(tetracarbonylcobaltate) {Co[CH₃C(O)NHCH₂CH₂CH₂Si(OCH₂CH₂)₃N]₆}[Co(CO)₄]₂ (VI), respectively. In acetonitrile, tetracarbonylcobaltate anions of compound VI are oxidized with atmospheric oxygen and moisture to cobalt hydroxocarbonate, giving a carbonate gel (VII).     

Rhodium(I) phosphine complexes containing bidentate unsaturated thio ligands: II. Reactions with O2 and H2

The rhodium(I) complexes (Ph₃P)₂Rh[Me₂NC(S)NC(S)NMe₂], (Ph₃P)₂Rh[SC(S)NMe₂] and (Ph₃P)₂Rh[PhNC(S)NMe₂] react with O₂ to give 1/1 dioxygen adducts. In solution, trans-(Ph₃P)₂Rh(O₂)[Me₂NC(S)NC(S)NMe₂], cis- and trans-(Ph₃P)₂Rh(O₂)[SC(S)NMe₂] and cis- and trans-(Ph₃P)₂Rh(O₂)[PhNC(S)NMe₂] are observed. For (Ph₃P)₂Rh(O₂)[PhNC(S)NMe₂], there is a solvent effect on the initial cis—trans ratio and the rate of O=PPh₃ formation. In C₆H₆, O=PPh₃ formation from (Ph₃P)₂Rh(O₂)[PhNC(S)NMe₂] is inhibited by additional PPh₃.The reaction of (Ph₃P)₂Rh[Ph₂PC(S)NPh] with O₂ in the presence of additional PPh₃ gives O=PPh₃ and cis-(Ph₃P)₂Rh(O₂)[Ph₂P(O)C(S)NPh] as the only products. The same complex also can be prepared from (Ph₃P)₂Rh[Ph₂P(O)C(S)NPh] and O₂.Only (Ph₃P)₂Rh[PhNC(S)NMe₂] reacts with H₂ at room temperature to give (Ph₃P)₂RhH₂[PhNC(S)NMe₂], which is a catalyst for cyclohexene hydrogenation.     

Reaktionen von Silylphosphanen mit Schwefel

Reactions of Silylphosphines with Sulphur We report about reactions of Me₂P? SiMe₃ 2 , MeP(SiMe₃)₂ 3 , (Me₃Si)₃P 4 , P₂(SiMe₃)₄ 5 , and (Me₃Si)₃P₇ 1 with elemental sulphur. Without using a solvent 2 reacts very vigorously. The reactions with 3 and 4 show less reactivity which is even more reduced with 5 and 1 . With equivalent amounts of sulphur the reactions with 2 , 3 , 4 lead to compounds with highest content of sulphur. These compounds are Me₃SiS? P(S)Me₂ 9 from 2 , (Me₃SiS)₂P(S)Me 13 from 3 and (Me₃SiS)₃P(S) 16 from 4 . Besides, the by-products (Me₃Si)₂S 8 , P₂Me₄ 7 , and Me₂P(S)? P(S)Me₂ 11 can be obtained. The reactions of silylphosphines in a pentane solution run much slower so that the formation of intermediates can be observed. Reaction with 2 yields Me₃SiS? PMe₂ 6 and Me₂P(S)PMe₂ 10 , which lead to the final products in a further reaction with sulphur. From 3 (Me₃SiS)(Me₃Si)PMe 14 and (Me₃SiS)₂PMe 12 can be obtained which react with sulphur to (Me₃SiS)₂P(S)Me 13. 4 leads to the intermediates (Me₃SiS)(Me₃Si)₂P 18 , (Me₃SiS)₂(Me₃Si)P 17 , (Me₃SiS)₃P 15 yielding (Me₃SiS)₃P(S) 16 with excess sulphur. Depending on the molar ratio (P₂SiMe₃)₄ 5 reacts to (Me₃Si)₂P? P(SSiMe₃)(Sime₃), (Me₃SiS)(Me₃Si)P? P(SSiMe₃). (Diastereoisomer ratio 10:1), (Me₃SiS)₂P? P(SiMe₃)₂ and (Me₃SiS)₂P? P(SSiMe₃)(Sime₃). With the molar ratio 1:4 the reaction yields (Me₃SiS)₂P? P(SSiMe₃)₂ (main product), (Me₃SiS)₃P(S) and (Me₃SiS)₃P. All silylated silylphosphines tend to decompose under formation of (Me₃Si)₂S. (Me₃Si)₃P₇ reacts with sulphur at 20°C (15 h) under decomposition of the P₇-cage and formation of (Me₃SiS)₃P(S). The products of the reaction of 5 with sulphur in hexane solution (molar ratio more than 1:3) undergo readily further reactions at 60°C under cleavage of P? P bonds and splitting off (Me₃Si)₂S, leading to (Me₃SiS)₃P(S) and cage molecules like P₄S₃, P₄S₇, and P₄S₁₀ and P? S-polymers. (Me₃SiS)₃P(S) isi thermally unstable and decomposes to P₄S₁₀ and (Me₃Si)₂S. Sulphur-containing silylphosphines like (Me₃SiS)P(S)Me₂ react with HBr at ?78°C under formation of Me₃SiBr (quantitative cleavage of the Si? S bond) and Me₂P(S)SH, which reacts with HBr to produce H₂S and Me₂P(S)Br.     

Reactions of RSe− (R = Me,Ph) Groups in [RSeFe(CO)4I and [RSeCr(CO)5−]

The anionic [MeSeFe(CO)₄] and [MeSeCr(CO)₅] complexes were synthesized by reaction of [PPN][HFe(CO)₄] and [PPN][HCr(CO)₅] with MeSeSeMe respectively via nucleophilic cleavage of the Se-Se bond. The ease of cleavage of the Se-Se bond follows the nucleophilic strength of metal-hydride complexes. Methylation of [RSeCr(CO)₅^?] by the soft alkylating agent MeI resulted in the formation of neutral (MeSeMe)Cr(CO)₅ in THF at 0°C. In contrast, the [ICr(CO)₅^?] was isolated at ambient temperature. Reaction of [MeSeFe(CO)₄^?] or [MeSeCr(CO)₅^?] with HBF₄ yielded (CO)₃Fc(μ-SeMe)₂Fe(CO)₃ dimer and anionic [(CO )₅Cr (μ-SeMe)Cr(CO)₅^?] respectively, and no neutral (HSeMe)Fe(CO)₄ and (HSeMe)Cr(CO)₅ were detected spectrally (IR) even at low temperature. Reaction of NOBF₄ or [Ph₃C][BF₄] and [MeSeCr(CO)₅^?] resulted in the neutral monodentate (MeSeSeMe)Cr(CO)₅ complex. Addition of 1 equiv CpFe(CO)₂I to 2 equiv [MeSeCr(CO)₅^?] gave CpFe(CO)₂(SeMe) and the anionic [(CO)₅Cr(μ-SeMe)Cr(CO)₅^?] in THF at ambient temperature.     

Übergangsmetall-heteroallen-komplexe XVII .Reaktionen des aza-allyl-komplexes (ketenimin)Fe2(CO)6 mit phosphanen

The aza-allyl complex (ketene imine)Fe₂(CO)₆ (3a) reacts with phosphanes PR₃ to give substitution products of the type (ketene imine)Fe₂(CO)₅PR₃ (4a,b). In addition, the phosphane PMe₃ yields a ferrole complex (5). Phosphites react with complex 3a to form mono- and di-substitution products (ketene imine)- Fe₂(CO)₅P(OR)₃ (4c,d) and (ketene imine)Fe₂(CO)₄(P(OR)₃)₂ (6). Diphosphanes yield substituted complexes of type (ketene imine)Fe₂(CO)₄(μ-Ph₂P ^⌢ PPh₂) (7). The structures of (ketene imine)Fe₂(CO)₅PMe₃ (4a), the ferrole complex 5, and (ketene imine)Fe₂(CO)₄(ν-Ph₂PCH₂CH₂PPh₂) (7b) were determined by X-ray analysis.     

Mass spectra of organometallic compounds—VII; Organonitrogen derivatives of metal carbonyls

The positive-ion mass spectra of the following organonitrogen derivatives of metal carbonyls are discussed: (i) The compounds NC₅H₄CH₂Fe(CO)₂C₅H₅, NC₅H₄CH₂COMo(CO)₂C₅H₅, NC₅H₄CH₂W(CO)₃C₅H₅, NC₅H₄CH₂COMn(CO)₄, C₅H₁₀NCH₂CH₂Fe(CO)₂C₅H₅, (CH₃)₂NCH₂CH₂COFeCOC₅H₅ and (CH₃)₂NCH₂CH₂COMn(CO)₄ obtained from metal carbonyl anions and haloalkylamines, (ii) The isocyanate derivative C₅H₅Mo(CO)₃CH₂NCO; (iii) The arylazomolybdenum derivatives RN₂Mo(CO)₂C₅H₅ (R ? phenyl, p-tolyl, or p-anisyl); (iv) The compound (C₆H₅N)₂COFe₂(CO)₆ obtained from Fe₃(CO)₁₂ and phenyl isocyanate; (v) The N,N,N′,N′-tetramethylethylenediamine complex (CH₃)₂NCH₂CH₂N(CH₃)₂W(CO)₄. Further examples of eliminations of hydrogen, CO, and C₂H₂ fragments were noted. In addition evidence for the following more unusual processes was obtained: (i) Elimination of HCN fragments from the ions [NC₅H₄CH₂MC₅H₅]⁺ to give the ions [(C₅H₅)₂M]⁺ (M ? Fe, Mo and W); (ii) Conversion of C₅H₅Mo(CO)₃CH₂NCO to C₅H₅Mo(CO)₂CH₂NCO within the mass spectrometer; (iii) Elimination of N₂ from [RN₂MoC₅H₅]⁺ to give [RMoC₅H₅]⁺; (iv) Novel eliminations of HNCO, FeNCO, and C₆H₅NC fragments in the mass spectrum of (C₆H₅N)₂COFe₂(CO)₆; (v) Facile dehydrogenation of the N,N,N′,-N′-tetramethylethylenediamine ligand in the complex (CH₃)₂NCH₂CH₂N(CH₃)₂W(CO)₄.     

Isocyanide addition to MN2(CO)5(Ph2PCH2PPh2)2 and the formation of a four-electron doubly-bridging isocyanide

The reactions of Fe(CO)₅, Fe(CO)₄P(C₆H₅)₃, M(CO)₆ (M  W, Mo, Cr), and (CH₃C₅H₄Mn(CO)₃ with KH and several boron and aluminium hydrides were investigated. Iron pentacarbonyl was converted quantitatively to K⁺Fe(CO)₄-(CHO) by hydride transfer from KBH(OCH₃)₃ allowing isolation of [P(C₆H₅)₃]₂-Nⁿ⁺Fe(CO)₄(CHO)^? in 50% yield. Lower yields were obtained with LiBH(C₂H₅)₃, and other hydride sources gave little or no formyl product. The stability of Fe(CO)₄(CHO)^? in THP was found to depend on the cation, decreasing in the order [P(C₆H₅)₃]₂N⁺ > K⁺ > Na⁺ > Li⁺. No formyl complexes were isolated and no spectroscopic evidence for formyl formation was observed in the reactions of the other transition metal carbonyls with several hydride sources. Fe(CO)₄-P(C₆H₅)₃ gave K₂Fe(CO)₄ when treated with KHB(OCH₃)₃. When treated with LiBH(C₂H₅)₃, W(CO)₆ gave a mixture of HW₂(CO)₁₀^?and (OC)₅W(COC₂H₅)^?; the latter was methylated to give the carbene complex (OC)₅WC(OCH₃)C₂H₅.     

A convenient synthesis of (η-C8H8)UI2(THF)2 (THF = tetrahydrofuran), a precursor to monocyclooctatetraenyl uranium complexes

(COT)₂U (COT = η-C₈H₈) reacts in tetrahydrofuran (THF) with I₂ to give the monocyclooctatetraenyl compound (COT)UI₂(THF)₂ (I) which is transformed into (COT)UI₂(HMPA)₂ (II) upon addition of 2 equiv. of hexamethylphosphoramide. Treatment of I with Kacac (acac = MeCOCHCOMe), KC₅Me₅ and LiCH₂SiMe₃ give (COT)U(acac)₂ (III), (COT)(C₅Me₅)UI (IV) and [(COT)U(CH₂SiMe₃)₃]-[Li(THF)₃] (V), respectively.     

Haloalkyl complexes of the transition metals: IV. The formation of a cationic ylide complex of platinum(II) from a chloromethylplatinum(II) complex and the crystal structures of cis-[Pt(CH2PPh3)X(PPh3)2]I (X = Cl or I)

The reactions of Pt(PPH₃)₄ and Pt(C₂H₄)(PPh₃)₂ with CH₂ClI have been investigated. The product of the reaction of Pt(PPh₃)₄ with CH₂ClI is the cationic ylide complex cis-[Pt(CH₂PPh₃)Cl(PPh₃)2][I], whereas the reaction of Pt(C₂H₄)-(PPh₃)₂ gives the oxidative addition product Pt(CH₂Cl)I(PPh₃)₂. Reaction of cis- or trans-Pt(CH₂Cl)I(PPh₃)₂] with PPh₃ gives the complex cis-[Pt(CH₂PPh₃)-Cl(PPh₃)₂][I]. The structures of the complexes cis-[Pt(CH₂PPh₃X(PPh₃)₂][I] (where X = Cl or I) have been determined by X-ray crystallography. Both complexes crystalize in the monoclinic space group P2₁/n. For X = Cl a 1388.6(7), b 2026.7(10), c 1823.9(9) pm, β 96.51(2)° and R converged to 0.075 for 3542 observed reflections; structural parameters Pt-Cl 240(1), Pt-C(3) 212(2), Pt-P(2) (trans to Cl) 235(1) and Pt-P(1) (trans to CH₂PPh₃) 233(1) pm; Cl-Pt-C(3) 86.9(5), C(3)-Pt-P(2) 91.8(5), P(2)-Pt-P(1) 97.0(2) and P(1)-Pt-Cl 85.1(2)°. For X = I, a 1379.4(7), b 2044.4(10), c 1840.0(9) pm, β 96.09(2)° and R converged to 0.071 for 4333 observed reflections; structural parameters Pt-I 266(1), Pt-C(3) 212(2), Pt-P(2) (trans to I) 226(1) and Pt-P(1) (trans to CH₂PPh₃ 233(1) pm; I-Pt-C(3) 87.2(5), C(3)-Pt-P(2) 91.5(5), P(2)-Pt-P(1) 96.5(2) and P(1)-Pt-I 85.6(1)°. Some other complexes of the type cis-[Pt(CH₂PPh₃)X(PPh₃)₂]Y are also described.     

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.