54003-37-1

Upstream product

• 15226-74-1 dicobalt octacarbonyl 
• 143-66-8 sodium tetraphenyl borate 
• 22031-12-5 [2-((diphenylphospino)methyl)-2-methyl-1,3-propanediyl]bis[diphenylphosphine] 
• 37701-79-4 [1,1,1,-tris((diphenylphosphino)methyl)ethane]cobalt(I) chloride 
• 201230-82-2 carbon monoxide 
• 123-73-9 crotonaldehyde 

Relevant academic research and scientific papers

Chemistry of polyfunctional molecules. 133. X-ray crystal structural, solid-state 31P CP/MAS NMR, TOSS, 31P COSY NMR, and mechanistic contributions to the co-ordination chemistry of octacarbonyldicobalt with the ligands bis(diphenylphosphanyl)amine, Bis(diphenylphosphanyl)methane, and 1,1,1-Tris(diphenylphosphanyl)ethane

Co2(CO)8 reacts with bis(diphenylphosphanyl)-amine, HN(PPh2)2 (Hdppa, 1), in two steps to afford the known compound [Co(CO)(Hdppa-κ2P)2][Co(CO)4] · 2 THF (6a · 2 THF). The intermediate [Co(CO)2(Hdppa-κ2P) · (Hdppa-κP)] [Co(CO)4] · dioxane · n-pentane (5 · dioxane · n-pentane) was isolated for the first time and was characterized by X-ray analysis. The cation 5+ exhibits a slightly distorted trigonal-bipyramidal geometry. Detailed 31P-NMR investigations (solid-state CP/MAS NMR, TOSS, 31P-COSY, 31P-EXSY) showed that the additional tautomer [Co(CO)2(Hdppa-κ2P)(Ph2P-N=P(H)Ph 2-κP)]+ (5′+) is present in solution. The tautomer equilibrium is slow in the NMR time scale. In contrast to the solid state only tetragonal pyramidal species of 5 are found in solution. At -90°C there is slow exchange between the three diastereomeric species 5a+-5c+. Compound 5 forms [Co(CO) · (Hdppa-κ2P)2]BPh4 · THF (6b · THF) in THF with NaBPh4 under CO-Elimination. A X-ray diffraction investigation shows that the cation 6+ consists of a slightly distorted trigonal-bipyramidal co-ordination polyeder. However, a distorted tetragonal-pyramidal structure has been found for the cation 7+ of the related compound [Co(CO)(dppm)2][Co(CO)4] · 2THF (7 · 2 THF; dppm = bis(diphenylphosphanyl)methane, Ph2PCH2PPh2). A comparison with the known [8] trigonal-bipyramidal stereoisomer, ascertained for 7+ of the solventfree 7, is described. In solutions of 6a · 2 THF and 7 · 2 THF 13C{1H}- and 31P{1H}-NMR spectra indicate an exchange of all CO and organophosphane molecules between cobalt(I) cation and cobalt(-I) anion. A concerted mechanism for the exchange process is discussed. CO elimination leads to discontinuance of the cyclic mechanism by forming binuclear substitution products such as the isolated Co2(CO)2 · (μ-CO)2(μ-dppm)2 · 0.83 THF (8 · 0.83 THF), which was characterized by spectroscopy and X-ray analysis. For_the dissolved [Co(CO)2CH3C(CH2PPh2) 3][Co(CO)4] · 0.83 n-pentane (9 a · 0.83 n-pentane) no CO and triphos exchange processes between the cation and the anion are observed. Metathesis of 9a · 0.83 n-pentane with NaBPh4 yields [Co(CO)2CH3C(CH2PPh2) 3]BPh4 (9b) which has been characterized by single-crystal X-ray analysis. The cation shows a small distorted tetragonal-pyramidal structure.

η4-Coordination of dienes and heterodienes to the tripodcobalt(I) template [CH3C(CH2PPh2)3CO]+: Synthesis, structure, and dynamics

CH3C(CH2PPh2)3CoCl (1) is easily accessible from CH3C(CH2PPh2)3CoCl2 by reduction with activated zinc powder. Upon dehalogenation with TlPF6, 1 reacts with dienes to give [tripodCo(I)-(η4- diene)]+ (2). The heterodienes acrolein and methyl vinyl ketone produce the analogous η4-heterodiene compounds 3. When crotonaldehyde is used as the potential η4-diene ligand, decarbonylation is observed leading to [tripodCo(I)-(CO)2]+ (4). Reaction of [tripodCo(aq)](BF4)2 with allyl mercaptan produces [tripodCO(I)-(η4-thioacrolein)]+ (3a) through dehydrogenation of the ligand precursor. 1,2-Diketones such as benzil and phenanthrenequinone do not coordinate in a η4 fashion but rather generate η2-coordinate enediolato ligands by an electron-transfer process, resulting in compounds of the type {tripodCo(III)-[η2-RC(O)=C(O)R]}+ (5). All the compounds have been characterized by standard analytical and spectroscopic techniques, including X-ray analysis in some cases. Compounds 4 and 5 show trigonal-bipyramidal coordination in the solid state, whereas the coordination polyhedra in compounds 2 and 3 are better described as square- pyramidal. While a minimum of two phosphorus resonances might be expected for each of these coordination geometries, only one time-averaged signal is normally observed, only with the η4-coordinated heterodienes acrolein, methyl vinyl ketone, and thioacrolein present in 3 is there a resolution of the signals of the three chemically distinct phosphorus nuclei at low temperatures. By 31P-NMR line-shape analysis, the activation barriers for the rotational reorientation of the heterodienes are found to be around ΔH(≠)=47 kJmol-1 for all three compounds 3.

PARAMAGNETIC CARBONYL COBALT(II) COMPLEXES. MOLECULAR STRUCTURE OF BROMOCARBONYL-1,1,1-TRIS(DIPHENYLPHOSPHINOMETHYL)ETHANECOBALT(II) TETRAPHENYLBORATE

Carbon monoxide or cyclohexyl isonitrile (L) react with the dinuclear five-coordinated derivatives of 1,1,1-tris(diphenylphosphinomethyl)ethane, (triphos), (BPh4)2 (X=halide) to give complexes of formula BPh4.The latter are rare examples of paramagnetic cobalt(II) carbonyl complexes.The molecular structure of 1/a with cell dimensions a 20.225(8), b 20.664(9), c 13.301(5); β 97.24(5) deg, Dc=1.338 gcm-3 for Z=4.Full-matrix least squares refinement led to the conventional R factor of 0.057 for 3648 observed reflections.The molecular structure consists of five-coordinate + cations of intermediate geometry and BPh4- anions.