58092-22-1

Upstream product

• 15226-74-1 dicobalt octacarbonyl 
• 95608-78-9 (C₆H₅)Br₂PMn(CH₃C₅H₄)(CO)2 
• 72868-86-1 phenylphosphine pentacarbonylmolybdenum⁽⁰⁾ 
• 33454-82-9 lithium trifluoromethanesulfonate 
• 14878-28-5 sodium tetracarbonyl cobaltate 
• 106733-98-6 Co4(CO)9(μ4-PPh)2{μ-C(OMe)CH3} 
• 106733-92-0 {Co4(CO)9(μ4-PPh)2C(O)H}Li 
• 644-97-3 Dichlorophenylphosphine 
• 13463-40-6 iron pentacarbonyl 
• 106733-94-2 {Co4(CO)9(μ4-PPh)2C(O)D}Li 
• 14878-26-3 potassium tetracarbonylcobaltate 

Downstream Products

• 105969-44-6 Co₄(CO)8(PC₆H₅)2(CH₂(P(C₆H₅)2)2) 
• 100044-09-5 Co₄(CO)8(PC₆H₅)2(C₂H₄(P(C₆H₅)2)2) 
• 105969-46-8 Co₄(CO)8(PPh)2(1,3-bis(diphenylphosphino)propane) 
• 105969-45-7 Co4(CO)9(η1-1,3-bis(diphenylphosphino)propane) 

Relevant academic research and scientific papers

Reaction of bis(dimethylphosphino)ethane with the tetracobalt cluster Co4(CO)10(μ4-PPh)2; synthesis, structure, and solution dynamics of Co4(CO)8(μ4-PPh)2(dmpe)

The reaction of the tetracobalt cluster Co4(CO)10(μ4-PPh)2 (1) with the bidentate ligand 1,2-bis(dimethylphosphino)ethane (dmpe) gives the disubstituted cluster Co4(CO)8(μ4-PPh)2(dmpe) (3) in high yield.The dmpe ligand is bond to a single cobalt atom in a chelating fashion as determined by FT-IR and NMR (31P and 13C) spectroscopy and single crystal X-ray crystallography.Co4(CO)8(μ4-PPh)2(dmpe)*1/2 toluene crystallizes in the triclinic space group P1 with a 11.673(1), b 15.986(5), c 20.276(7) Angstroem, α 94.40(3), β 106.28(2), γ 94.89(2) deg, V 3599(2) Angstroem3 and Z = 4.Block-cascade least squares refinement yielded R = 0.0521 for 6830 reflections.The temperature-dependent 13C NMR spectra of 3 reveal to distinct fluxional processes which serve to equilibrate the carbonyl ligands about the cluster polyhedron.The stability of 3 under different conditions has been examined by Cylindrical Internal Reflectance (CIR) spectroscopy.In benzene solution 3 is stable under 250 psi of H2 at 150 deg C; partial decomposition to Co(CO)4- is observed using CO and H2/CO under analogous conditions.

μ3-P- UND μ3-As-VERBRUECKTE CLUSTER ALS LIGANDEN

The trihalophosphane complexes LnM-PHal3 (LnM = Cp(CO)2Mn, (CO)5Cr, (CO)5W; Hal = Cl, Br), upon treatment with Co2(CO)8, mainly yield clusters of the type Co3(CO)9(μ4-P)MLn with the (μ3-P)C

Stoichiometric molecular single source precursors to cobalt phosphides

Crystalline cobalt phosphides were synthesized by using three different, low oxidation-state organometallic clusters as precursors, [Co 4(CO)10(μ-dppa)], [Co4(CO) 10(μ4-PPh)2] and [Co4

Reactivity of the Binuclear Compound, CpMnCo(CO)5PPhH (Cp = n5-Cyclopentadienyl, Ph = Phenyl) and Synthesis of Higher Nuclear Compounds

The dehydrogenation reaction of CpMnCo(CO)5PPhH with Fe3(CO)12, Ru3(CO)12, Co2(CO)8, and CpMn(CO)8 were performed both in benzene and toluene medium and the compounds CpCo3(CO)6(μ8-PPh) and Cp2Co4(CO)4(μ2-CO)(μ4-PPh)2 along with few other already known products were isolated.The compounds were characterised by elemental analysis, ir, 1H nmr and mass spectral studies.

Site selectivity and competitive CO attack in Co4(CO)10(μ4-PPh)2 using methanolic

The reaction between the tetracobalt cluster Co4(CO)10(μ4-PPh)2 (1) and (1.1 equivalents of a 1.3 M solution in MeOH) has been examined in THF at -78 deg C.Low temperature IR analysis reveals the presence of both the hydroxycarbonyl

Carbon-13 relaxation and reorientational dynamics in a bicapped tetracobalt cluster

13C spin-lattice (T1) relaxation times and nuclear Overhauser enhancements of the phenyl (ortho, meta, and para) carbons in the tetracobalt cluster Co4(CO)10(μ4-PPh)2 were measured as a function of temperature in CDCl3. Three of the resonances exhibit triplet structure, indicating significant 31P?31P interaction between the phosphinidene capping ligands. The rotational diffusion constants Ds (=D∥ + R) and D⊥ derived from the T1's reveal that the phenyl spinning rate (Ds) is approximately twice as rapid as molecular tumbling (D⊥) at all temperatures. Comparison with the experimental diffusion constants in other systems suggests strongly that the phenyl rings do not undergo internal rotation (R ≈ 0). This immobility is explained only partially by steric factors in the molecule. Comparison of the experimental results with diffusion constants calculated by the Perrin stick and Hu-Zwanzig slip models shows that the reorientational dynamics of the cluster is not well described by either of these limiting theories. Diffusion constants calculated by the newer Hynes-Kapral-Weinberg model provide the best agreement with the experimental results.

Nucleophilic additions to carbonyl ligands on tetracobalt clusters. Formation of polynuclear formyl and carbene complexes

The tetracobalt cluster Co4(CO)10(μ4-PPh)2 (I) undergoes facile reductive decarbonylation to afford the bridged hydride Co4(CO)9(PPh)2(μ-H)- in quantitative yields upon the treatment with various types of borohydrides at 25°C. However, when the reductions are carried out at -78°C, a transient intermediate can be detected and its structure shown to be the corresponding formyl derivative Co4(CO)9(PPh)2CHO- (III) from its IR spectrum and 1H and 13C NMR spectra. The formation of the formyl intermediate III is confirmed by deuterium-labeling studies, and its spontaneous decarbonylation to the μ-hydride is described. Nucleophilic addition to a CO ligand as a route to the formyl intermediate is demonstrated by the generation of the corresponding acyl analogues in excellent yields following the treatment of I with methyl- and n-butyllithium. The formyl and acetyl tetracobalt clusters are efficiently trapped by O-alkylation with methyl inflate to afford the carbene derivatives Co4(CO)9(PPh)2[μ-C(OMe)H] and Co4(CO)9(PPh)2[μ-C(OMe)Me], respectively. Nucleophilic addition to I followed by alkylation to afford these tetracobalt carbene derivatives is thus analogous to the behavior of the triosmium cluster Os3(CO)12 recently reported by Kaesz and co-workers. The acid-catalyzed 1,2-elimination of methanol from the carbene cluster Co4(CO)9(PPh)2[μ-C(OMe)Me] yields the vinylidene cluster Co4(CO)9(PPh)2(μ-C=CH2), which is also produced in high yields when the acetyl cluster is treated with trifluoroacetic anhydride. The molecular structpres of Co4(CO)9(PPh)2[μ-C(OMe)Me] and the vinylidene derivative are established by X-ray crystallography. Co4(CO)9(PPh)2[μ-C(OMe)Me] crystallizes in the monoclinic space group P21/c with a = 16.465 (2) A?, b = 23.987 (3) A?, c = 15.775 (2) A?, β = 112.61 (1)°, V = 5752 A?3, and Z = 8. Co4(CO)9(PPh)2(μ-C=CH2) crystallizes in the monoclinic space group P21/n with a = 9.954 (1) A?, b = 12.865 (3) A?, c = 10.270 (1) A?, β = 98.88 (1)°, V = 1299 A?3, and Z = 2. Reactivity studies of the formyl and the various carbene ligands bound to the tetracobalt cluster are described.

Oxidation-reduction and the electrocatalytic ligand substitution of tetracobalt clusters

The capacity of polynuclear clusters to undergo multiple oxidation and reduction is probed with a series of bicapped tetracobalt carbonyls derived from the phenylphosphinidene-bridged Co4(CO)10(μ4-PPh)2 (I). The redox behavior of I and its derivatives Co4(CO)10-x(μ4-PPh)2L x, where L is a mono- or diphosphine, is initially examined by a combination of electrochemical methods including cyclic voltammetry, linear sweep microvoltammetry, and polarography. All the techniques reveal a consistent trend for the oxidation of the tetracobalt cluster to be increasingly facilitated upon successive phosphine substitution (x = 0, 1, 2, 3, and 4); but reduction follows the opposite trend. The anion radical derived from the 0/-1 redox couple of the tetracobalt cluster I is shown to be substitutionally labile. The latter allows a facile ligand substitution to occur under mild conditions when a small cathodic current is passed through a solution of the cluster I containing various phosphorus(III) nucleophiles. The mechanism of the electrocatalytic process is discussed in the light of electron-transfer catalysis applicable to other mononuclear and polynuclear metal carbonyls.

Structures and mechanism of multiple ligand substitutions in bicapped tetracobalt clusters

The planar tetracobalt carbonyl cluster with a pair of μ4-phosphinidene caps Co4(CO)10(μ4-PPh)2 undergoes ready ligand substitution with trimethyl phosphite thermally to afford the mono, bis, tris, and tetrakis derivatives. The molecular structures of the substitution products by X-ray crystallography establish the stepwise introduction of phosphites at separate cobalt centers. Electronic and steric effects play important roles in the sequential introduction and the stereochemical disposition of the phosphite ligands in the bis-, tris-, and tetrakis-substitution products. The kinetics and activation parameters indicate that the mono- and bis-substitutions occur primarily via an associative mechanism, whereas a dissociative process is dominant in the tris- and tetrakis-substitutions. The fluxional behavior of the carbonyl ligands, as observed by the temperature-dependent 13C NMR spectra, is in accord with the extensive stereomutation of ligands during substitution - particularly in those steps leading to the tris and tetrakis derivatives. The changeover in the mechanism of ligand substitution with the extent of phosphite substitution of the tetracobalt cluster is discussed.

Chemical Redox Reactions of Trinuclear Clusters

The clusters ECo3(CO)9 (E = S, PPh) can be converted with one electron oxidants to their cations which are only stable in solution.Reduction of EFeCo2(CO)9 (E = S, PPh) with sodium naphthalenide or cobaltocene produces the anions which are stable as PPN(+) or CoCp2(+) salts.The clusters RPCo3(CO)9 (R = Ph, NEt2, OBu) react with iodine to form the tetranuclear clusters (RP)2Co4(CO)10. - Key words: Organometallic Clusters, Chemical Redox Reactions