Some observations on the systems Co2(CO)8/sodium amalgam and Hg[Co(CO)4]2/sodium amalgam,and the effect of added LiBr

Co₂(CO)₈ and Hg[Co(CO)₄]₂ react sodium amalgam and/or mercury in ethereal solvents to give a variety of products. On treatment with aqueous M(o-phen)₃Cl₂(M  Fe, Ni), the anions [Co(CO)₄^?, [Co₃(CO)₁₀]^?, {Hg[Co(CO)₄]₃}^? and {Hg[Co(CO)₄]₂Cl}^? could be isolated as their [M(o-phen)₃]²⁺ salts. The effect of LiBr on the reacting systems was also investigated and the anion {Hg[Co(CO)₄]₂Br}^? isolated.     

Alternating copolymerization of propylene oxide with carbon monoxide catalyzed by Co complex and Co/Ru complexes

Co₂(CO)₈ catalyzes the ring‐opening copolymerization of propylene oxide with CO to afford the polyester in the presence of various amine cocatalysts. The ¹H and ¹³C{¹H} NMR spectra of the polyester, obtained by the Co₂(CO)₈–3‐hydroxypyridine catalyst, show the following structure ? [CH₂? CH(CH₃)? O? CO]_n? . The Co₂(CO)₈–phenol catalyst gives the polyester, which contains the partial structural unit formed through the ring‐opening copolymerization of tetrahydrofuran with CO. The bidentate amines, such as bipyridine and N,N,N′,N′‐tetramethylethylenediamine, enhance the Co complex‐catalyzed copolymerization, which produces the polyester with a regulated structure. Acylcobalt complexes, (RCO)Co(CO)_n (R = Me or CH₂Ph), prepared in situ, do not catalyze the copolymerization even in the presence of pyridine. This suggests that the chain growth involves the intermolecular nucleophilic addition of the OH group of the intermediate complex to the acyl–cobalt bond, forming an ester bond rather than the insertion of propylene oxide into the acyl–cobalt bond. Co₂(CO)₈? Ru₃(CO)₁₂ mixtures also bring about the copolymerization of propylene oxide with CO. The molar ratio of Ru to Co affects the yield, molecular weight, and structure of the produced copolymer. The catalysis is ascribed to the Ru? Co mixed‐metal cluster formed in the reaction mixture. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4530–4537, 2002     

Permetalloplumbanes: Preparation of [Pb{Co(CO)3(L)}4] and [Pb{Fe(CO)2(NO)(L)}4].: Complexes containing four transition metal to lead bonds (L = tertiary arsine,phosphine or phosphite).

The sole and unexpected products from the reactions of a variety of lead (II) and lead (IV) compounds with [Co₂(CO)₆(L)₂] complexes (L = tertiary arsine, phosphine, or phosphite) in refluxing benzene solution are the blue, air-stable percobaltoplumbanes [Pb{Co(CO)₃(L)}₄]. These have also been obtained from the reaction of Na[Co(CO)₃(L)] (L  PBu₃ⁿ) with lead (II) acetate which with Na[Fe(CO)₂(NO)(L)] forms the isoelectronic [Pb{Fe(CO)₂(NO)(L)}₄] [L  P(OPh)₃]. The IR spectra of the complexes in the v(CO) and v(NO) regions are consistent with tetrahedral PbCo₄ or PbFe₄ fragments, trigonal bipyramidal coordination about the cobalt or iron atoms and linear PbCoAs, PbCoP, or PbFeP systems. Unlike [Pb{Co(CO)₄}₄], our complexes do not dissociate to [Co(CO)₃(L)]^? or [Fe(CO)₂(NO)(L)]^? ions when dissolved in donor solvents.     

Bildung siliciumorganischer Verbindungen. 80. Die Si-Metallierung von 1,3,5-Trisilacyclohexanen mit Übergangsmetallkomplexen

Formation of Organosilicon Compounds. 80. Si-Metalation of 1,3,5-Trisilacyclohexanes by Means of Trisition Metal Complexes Several Si-transition metal-substituted 1,3,5-trisilacyclohexanes are reported. l-Bromo-1,3,5-trisilacyclohexane reacts with the metal carbonyl anions W(CO)₅cp^?, Mo(CO)₃cp-, Cr(CO)₃cp^?, Mn(CO)₃^?, Fe(CO)₂cp^?, or Co(CO)_4minus;, resp., yielding monosubstituted derivatives as 6, e. g.(cp = π-cyclopentadienyl). 1,3-Dibromo-1,3,5-trisilacyclohexane forms disubstituted compounds aa 7, e. g., with 2 moles of the metal carbonyl anions Fe(CO)₂cp^?, Mn(CO)₅^? or Co(CO)₄^?. Starting from (H₂c? SiHBr)₃ compound 13 is accessible by reaction with KCo(CO)₄. In the soluted compounds the metal carbonyl groups occupy the equatorial positions in the chair form of the six membered ring. The reaction of 13 with Co₂(CO)₈ yields 17 , whereas 6 preferrably forms 18 . Starting from (H₂C? SiH₂)3 the reaction with Co₂(CO)₂ preferrably yields 19. The reported compounds are crystalline, air – and moisture – sensitive. The reported formulae are assured by analysis, IR, and NMR investigations.     

Facile Access to Transition‐Metal–Carbonyl Complexes with an Amidinate‐Stabilized Chlorosilylene Ligand

Three transition‐metal–carbonyl complexes [V( L )(CO)₃(Cp)] ( 1 ), [Co( L )(CO)(Cp)] ( 2 ), and [Co( L₂ )(CO)₃]⁺[CoCO)₄]^? ( 3 ), each containing stable N‐heterocyclic‐chlorosilylene ligands ( L ; L =PhC(NtBu)₂SiCl) were synthesized from [V(CO)₄(Cp)], [Co(CO)₂(Cp)], and Co₂(CO)₈, respectively. Complexes 1 , 2 , 3 were characterized by NMR and IR spectroscopy, EI‐MS spectrometry, and elemental analysis. The molecular structures of compounds 1 , 2 , 3 were determined by single‐crystal X‐ray diffraction.     

Metallkomplexe mit anionischen Liganden von Elementen der 4. Hauptgruppe. IX. Zum komplexchemischen Verhalten von Trichlorstannid-und Trichlorgermid-Ionen gegenüber Komplexen von Übergangsmetallen in niedrigen Oxydationsstufen

Metal Complexes with Anionic Ligands of the Main Group IV Elements. IX. Reactions of Trichlorostannide and Trichlorogermide Ions with Complexes of Transition Metals in Low Oxidation States Carhonyl trichlorostannido- and carbonyl trichlorogermido-metalate complexes have been synthesized both by photochemical and thermical substitution reactions of [ECl₃]^? ions (E = Sn, Ge) with M(CO)₆, (M = Cr, Mo, W), Fe(CO)₅ Fe₃(CO)₁₂, Co₂(CO)₈, as well as with the metalcarbonyl derivatives (π-arene)M(CO)₃, (M = Cr, Mo), (h⁵-C₅,H₅,)V(CO)₄, Mn(CO)₅,Cl, Co(NO)(CO)₃, and Fe(NO)₂,(CO)₂. Mainly the bonding properties of the [ECl₃]^? ligands are discussed by means of i.r. spectroscopic investigations. The progress of the reactions and the necessary reaction conditions show that the nucleophilic properties oft both anions [ECl₃]^? are unexpectedly small. The slightly weaker hasicity of [SnCl₃]^? compared with [GeC1₃]^? arreared, when both anions were reacted with Co₂,(CO)₈, forming the substitution product. [Co₂,(CO)₇,SnCl₃]^? and the products of a “base reaction” Cl₃GcCo(CO)₄, and [Co(CO)₄]^?.     

Formation of the Salt‐like Complexes [Co{S2CC(PPh3)2}3][Co(CO)4]3 and [(CO)4Mn{S2CC(PPh3)2}][Mn(CO)5] from the Reaction of the Related Carbonyl Compounds with S2CC(PPh3)2

The betain‐like compound S₂CC(PPh₃)₂ ( 1 ), which is obtained from CS₂ and the double ylide C(PPh₃)₂, reacts with [Co₂(CO)₈] and [Mn₂(CO)₁₀] in THF to afford the salt‐like complexes [Co{S₂CC(PPh₃)₂}₃][Co(CO)₄]₃ ( 2 ) and [(CO)₄Mn{S₂CC(PPh₃)₂}][Mn(CO)₅] ( 3 ), respectively, in good yields. At both d⁶ cations 1 acts as a chelating ligand. Disproportionation reactions from formal Co⁰ into Co^III and Co^?I and from Mn⁰ into Mn^I and Mn^?I occurred with the removal of four or one carbonyl groups, respectively. The crystal structures of 2· 5.5THF and 3· 2THF are reported, which show a shortening of the C–C bond in the ligand upon complex formation. The compounds are further characterized by ³¹P NMR and IR spectroscopy.     

以钴羰基簇合物为前驱体制备的钴基催化剂上F-T反应性能简

以含羧酸配体的钴羰基簇合物Co₂（CO）₆HCCCOOH,Co₃（CO）₉CCH₂COOH,Co₄（CO）₁₀HCCCOOH 为前驱体,γ-Al₂O₃为载体,通过浸渍法制备了一系列催化剂;同时以Co（NO₃）₂作为前驱体制备了参比催化剂. 对制备的催化剂进行了费托反应性能评价,并用透射电子显微镜、氨程序升温脱附和傅里叶变换红外光谱等手段对催化剂进行了表征. 结果发现,不同前驱体制备的催化剂对载体上Co的分布具有明显影响,进而影响催化剂活性. 反应结果表明,不同前驱体制备的催化剂上CO转化率及C₅₊选择性顺序为Co₃（CO）₉CCH₂COOH > Co₂（CO）₆HCCCOOH > Co₄（CO）₁₀HCCCOOH > Co（NO₃）₂.     

A Cobalt(I) Pincer Complex with an η2‐Caryl−H Agostic Bond: Facile C−H Bond Cleavage through Deprotonation,Radical Abstraction,and Oxidative Addition

The synthesis and reactivity of a Co^I pincer complex [Co(?³P,CH,P‐P(CH)P^NMe‐iPr)(CO)₂]⁺ featuring an η²‐ C_aryl?H agostic bond is described. This complex was obtained by protonation of the Co^I complex [Co(PCP^NMe‐iPr)(CO)₂]. The Co^III hydride complex [Co(PCP^NMe‐iPr)(CNtBu)₂(H)]⁺ was obtained upon protonation of [Co(PCP^NMe‐iPr)(CNtBu)₂]. Three ways to cleave the agostic C?H bond are presented. First, owing to the acidity of the agostic proton, treatment with pyridine results in facile deprotonation (C?H bond cleavage) and reformation of [Co(PCP^NMe‐iPr)(CO)₂]. Second, C?H bond cleavage is achieved upon exposure of [Co(?³P,CH,P‐P(CH)P^NMe‐iPr)(CO)₂]⁺ to oxygen or TEMPO to yield the paramagnetic Co^II PCP complex [Co(PCP^NMe‐iPr)(CO)₂]⁺. Finally, replacement of one CO ligand in [Co(?³P,CH,P‐P(CH)P^NMe‐iPr)(CO)₂]⁺ by CNtBu promotes the rapid oxidative addition of the agostic η²‐C_aryl?H bond to give two isomeric hydride complexes of the type [Co(PCP^NMe‐iPr)(CNtBu)(CO)(H)]⁺.     

Stibinidene and Bismuthinidene as Two‐Electron Donors for Transition Metals (Co and Mn)

The reaction of stibinidene and bismuthinidene ArM [where Ar=C₆H₃‐2,6‐(CH=NtBu)₂; M=Sb ( 1 ), Bi ( 2 )] with transition metal (TM) carbonyls Co₂(CO)₈ and Mn₂(CO)₁₀ produced unprecedented ionic complexes [(ArM)₂Co(CO)₃]⁺[Co(CO)₄]^? and [(ArM)₂Mn(CO)₄]⁺[Mn(CO)₅]^? [where M=Sb ( 3 , 5 ), Bi ( 4 , 6 )]. The pnictinidenes 1 and 2 behaved as two‐electron donors in this set of compounds. Besides the M→TM bonds, the topological analysis also revealed a number of secondary interactions contributing to the stabilization of cationic parts of titled complexes.     

Reactivity of Cyanide and Thiocyanate Towards the Nitrosyl Carbonyl [Co(CO)3(NO)]

The reaction of equimolar amounts of [Co(CO)₃(NO)] and [PPN]CN, PPN⁺ = (PPh₃)₂N⁺, in THF at room temperature resulted in ligand substitution of a carbonyl towards the cyanido ligand presumably affording the complex salt PPN[Co(CO)₂(NO)(CN)] as a reactive intermediate species which could not be isolated. Applying the synthetic protocol using the nitrosyl carbonyl in excess, the title reaction afforded unexpectedly the novel complex salt PPN[Co₂(μ-CN)(CO)₄(NO)₂] ( 1 ) in high yield. Because of many disorder phenomena in crystals of 1 the corresponding NBu₄⁺ salt of 1 has been prepared and the molecular structure of the dinuclear metal core in NnBu₄[Co₂(μ-CN)(CO)₄(NO)₂] ( 2 ) was determined by X-ray crystal diffraction in a more satisfactory manner. In contrast to the former result, the reaction of [PPN]SCN with [Co(CO)₃(NO)] yielded the mononuclear complex salt PPN[Co(CO)₂(NO)(SCN-κN)] ( 3 ) in good yield whose molecular structure in the solid was even determined and its composition additionally confirmed by spectroscopic means.     

[Co4P2(PtBu2)2(CO)8] und [{Co(CO)3}2P4tBu4] aus Co2(CO)8 und tBu2P–P=P(Me)tBu2

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XIX. [Co₄P₂(P^tBu₂)₂(CO)₈] and [{Co(CO)₃}₂P₄^tBu₄] from Co₂(CO)₈ and ^tBu₂P–P=P(Me)^tBu₂ Co₂(CO)₈ reacts with ^tBu₂P–P=P(Me)^tBu₂ yielding the compounds [Co₄P₂(P^tBu₂)₂(CO)₈] ( 1 ) and [{η^2tBu₂P=P–P=P^tBu₂}{Co(CO)₃}₂] ( 2 a ) cis, ( 2 b ) trans. In 1 , four Co and two P atoms form a tetragonal bipyramid, in which two adjacent Co atoms are μ₂‐bridged by ^tBu₂P groups. Additionally, two CO groups are linked to each Co atom. In 2 a and 2 b , each of the Co(CO)₃ units is η²‐coordinated to the terminal P₂ units resulting in the cis‐ and trans‐configurations 2 a and 2 b . 1 crystallizes in the orthorhombic space group Pnnm (No. 58) with a = 879,41(5), b = 1199,11(8), c = 1773,65(11) pm. 2 a crystallizes in the monoclinic space group P2₁/n (No. 14) with a = 875,97(5), b = 1625,36(11), c = 2117,86(12) pm, β = 91,714(7)°. 2 b crystallizes in the triclinic space group P 1 (No. 2) with a = 812,00(10), b = 843,40(10), c = 1179,3(2) pm, α = 100,92(2)°, β = 102,31(2)°, γ = 102,25(2)°.     

Magnetic and Spectral Properties of Heterotrinuclear Acetates [Ru2Co(μ3-O)(μ-CH3CO2)6(Py)3]n+ (n = 0 or 1)

The preparation and physical properties of the new heterotrinuclear acetates, [Ru₂CO(μ₃-O)(μ-CH₃CO₂)₆(Py)₃] (Ru₂Co(II)) and [Ru₂Co(μ₃-O)(μ-CH₃CO₂)₆(Py)₃)l₃ (Ru₂Co(III), Py = pyridine), are reported. Three reversible one-electron-redox waves are observed at 1.19, 0.40, and ?1.24 V vs Ag/Ag⁺ electrode for Ru₂Co(lI) in CH₂Cl₂. The complexes of Ru₂Co(II) and Ru₂Co(III) show an intense visible absorption at 570 (? 5950 M^?1 cm^?1) and 551 nm (? 7240 M^?1 cm^?1), respectively. The magnetic susceptibilities of both complexes were also measured from 4.2 to 300 K. The resulting least-squares fit parameters for Ru₂Co(II) areJ_RuCo = ?9 cm^?1, J_RuRu = ?22 cm^?1, g_Co, = g_Ru= 2.19.     

Ge2Co6(CO)20: Ein Ge‐Co‐Cluster ausgehend von gelöstem GeBr

Ge₂Co₆(CO)₂₀: A Ge‐Co Cluster Compound from Solubilized GeBr The Ge‐Co cluster Ge₂Co₆(CO)₂₀ is synthesized from a reaction of a GeBr solution with Co₂(CO)₈. Isolation of suitable crystals allows the determination of the crystal structure of Ge₂Co₆(CO)₂₀, being the lacking member in the row GeCo₄(CO)₁₄ – Ge₂Co₆(CO)₂₀ – Ge₃Co₈(CO)₂₆.     

Synthèse rationelle de clusters mixtes à trois au quatre métaux differents et contenant le ligand Ph2PCH2PPh2 (dppm)

Reaction of PdPtCl₂(dppm)₂ with Co(CO)₄^? or Mn(CO)₅^? affords the tetrametallic clusters PdPtCo₂(CO)₇(dppm)₂ and PdPtMn₂(CO)₉(dppm)₂. The cobalt cluster reacts with iodide to give PdPtCoI(CO)₃(dppm)₂ which upon reaction with Fe(CO)₃NO^? or Mn(CO)₅^? yields PdPtFeCo(CO)₆NO(dppm)₂ and PdPtMnCo(CO)₈(dppm)₂, respectively.     

Heteronukleare Komplexverbindungen mit Metall—Metall-Bindungen. VIII. Neue heterodinukleare Komplexe mit Bindungen zwischen Kupfer(I) und Mangan(–I), Eisen(–I) oder Cobalt(–I)

Heteronuclear Coordination Compounds with Metal—Metal Bonds. VIII. New Heterodinuclear Complexes with Bonds between Copper(I) and Manganese(?I), Iron(?I), or Cobalt(?I) [(en)Cu? Mn(CO)₅] ( 1a ), [(dien)Cu? Mn(CO)₅] ( 1b ), [(en)Cu? Fe(CO)₃(NO)] ( 2a ), [(dien)Cu? Fe(CO)₃(NO)] ( 2b ), [(en)Cu? Co(CO)₄] ( 3a ), and [(dien)Cu? Co(CO)₄] ( 3b ) are new heterobinuclear metal—metal bonded complexes. The geometry of the [Mn(CO)₅]^?, [Fe(CO)₃(NO)]^?, and [Co(CO)₄]^? ions is distorted only to a less extend in accord with a heteropolar bond to copper.     

Cyclic voltammetry of silyl- and stannyl-tricobalt cluster compounds

The electrochemical behavior of the clusters PhM′Co₃(CO)_n (M′ = Si, n = 11 and M′ = Sn, n = 12) has been examined via cyclic voltammetry in CH₂Cl₂ solution. In both cases the radical anions PhM′Co₃(CO)_n? are unstable, rearranging to Co(CO)₄ and other products. However, for the silicon compound, where there is one formal cobalt—cobalt bond, the radical anion is sufficiently stable to allow for detection of anion reoxidation at medium scan speeds. The half-life of PhSiCo₃(CO)₁₁? has been calculated as 2.3 s at 25°C.     

Über Reaktionen oxygenierter Kobalt(II)-Komplexe. IX. Oxydative Eigenschaften von Tetrakis(äthylendiamin)-μ-peroxo-μ-hydroxo-dikobalt(III)

Reactions of oxygenated cobalt(II) complexes. IX. Oxidative properties of tetrakis(ethylenediamine)-μ-peroxo-μ-hydroxo-dicobalt(III)

1 VIII s. [1].

[(en)₂Co(O₂, OH)Co(en)₂]³⁺ ( a ) reacts with I^? in acidic aqueous solution according to: Co^III(O₂, OH)Co^III + 21^? + 5H⁺ ? 2Co^III + 3H₂O + I₂. Using I^? in excess first order rate constants are obtained which, to a first approximation, are independent of [I^?]. Comparison with kinetic data of deoxygenation of [(en)₂Co(O₂, OH)Co(en)₂]³⁺ under analogous conditions suggests that both reactions have the same rate determining step. The singly bridged species [(en)₂(H₂O)CoO₂Co(H₂O) (en)₂]⁴⁺ is shown to be the reactive intermediate in the iodide oxidation (Schema 2).     

Synthese et reactivite d'un complexe diene-fertricarbonyle derive du phenyl-1-dimethyl-3,4-phosphole

The complex (DMPP)Fe₂(CO)₇ in which DMPP (1-phenyl-3,4-dimethylphosphole) is η⁴-coordinated with Fe(CO)₃ through its diene and η¹-coordinated with Fe(CO)₄ through its phosphorus atom is selectively decomplexed at phosphorus to give (DMPP)Fe(CO)₃ by reaction with AlCl₃ followed by NH₄OH. This new η⁴-complex (DMPP)Fe(CO)₃ can be oxidized, sulfurized and quaternized at phosphorus by H₂O₂, S₈, and PhCH₂Br and MeI, respectively, as an ordinary phosphine without decomplexation of the diene. As a free phosphole, this complex also gives a ring-expanded product by reaction with benzoyl chloride, water and Et₃N. In the presence of some metallic salts such as (PhCN)₂PdCl₂, it loses CO to give the bimetallic sandwich [(DMPP)Fe(CO)₂]₂. It can also give some new bimetallic complexes such as [(DMPP)Fe(CO)₃]W(CO)₅ by complexation of the phosphorus lone pair by W(CO)₅(THF).