151925-26-7

Upstream product

• 82363-89-1 (diphenylphosphino)acetophenone 

Downstream Products

• 152018-35-4 CoCl((C₆H₅)2PCH₂C(O)C₆H₅)2⁽¹⁺⁾*PF₆^(1-)={CoCl((C₆H₅)2PCH₂C(O)C₆H₅)2}PF₆ 
• 151925-30-3 Co₂(CO)6((C₆H₅)2PCH₂C(O)C₆H₅)2 
• 152978-02-4 {CoI₂((C₆H₅)2PCH₂C(O)(C₆H₅))2} 
• 151925-27-8 {CoBr₂((C₆H₅)2PCH₂C(O)(C₆H₅))2} 

Relevant academic research and scientific papers

Complexes of functional phosphines. 23. PPh3 and β-ketophosphine complexes of cobalt(II). Crystal and molecular structures of CoCl2[Ph2PCH2C(O)Ph]2 and Co2(CO)6[Ph2PCH2C(O)Ph]2 and of the trinuclear, mixed-metal complex [(Ph3P)2 ...

Full title: Complexes of functional phosphines. 23. PPh3 and β-ketophosphine complexes of cobalt(II). Crystal and molecular structures of CoCl2[Ph2PCH2C(O)Ph]2 and Co2(CO)6[Ph2PCH2C(O)Ph]2 and of the trinuclear, mixed-metal complex [(Ph3P)2Ag(μ-Cl)2Co(μ-Cl) 2Ag(PPh3)2]·0.5OEt2. The solution chemistry of cobalt(II) ketophosphine complexes CoX2[Ph2PCH2C(O)Ph]2 (1a, X = Cl; 1b, X = Br; 1c, X = I) has been examined and compared to that of [CoX2(PPh3)2] (2a, X = Cl; 2b, X = Br; 2c, X = I). All the complexes undergo a tetrahedral-octahedral equilibrium in methanol. This is facilitated by solvent coordination rather than by the ligand's keto functions. Some degree of ligand displacement also occurs. The crystal structure of 1a has been elucidated, showing a pseudotetrahedral cobalt(II) geometry. A long interligand hydrogen-bond, not present in powder samples, is observed between the methylene group of a Ph2PCH2C(O)Ph ligand and the ketone function of the other Ph2PCH2C(O)Ph ligand. 1a reacts with Na[Co(CO)4] to afford the crystallographically characterized, metal-metal bonded centrosymmetric complex Co2(CO)6[Ph2PCH2C(O)Ph]2 (5) (Co-Co = 2.666(1) A?). The reactivity of 1a with AgBF4 and TlPF6 has also been examined and compared to that of 2a where the latter is reacted in the presence and absence of excess phosphine. Notable reaction products include the square planar cobalt(II) complex [Co{Ph2PCH2C(O)Ph}{Ph2PCH 2C(O)Ph}Cl]PF6 (6), which slowly transforms in solution to the octahedral complex [Co{Ph2PCH2C(O)Ph}2{Ph2PCH 2C(O)Ph}Cl]PF6 (7). Reaction with AgBF4 under similar conditions affords the silver phosphine complex Ag{Ph2PCH2C(O)Ph}2Cl (8). 2a reacts with AgBF4 to give [Ag-(PPh3)2]BF4, but additionally in the presence PPh3 gives (Ph3P)2Ag(μ-Cl)2Co(μ-Cl) 2Ag(PPh3)2 (13). The latter formulation involving a central CoCl42- core, and an almost linear Ag-Co-Ag arrangement has been confirmed by single-crystal X-ray diffraction. The solid state structures of 1a, 5, and 13·0.5OEt2 have been determined by single-crystal X-ray analysis. 1a crystallizes in the monoclinic space group P21/c with Z = 4 in a unit cell of dimensions a = 10.985(2) A?, b = 17.236(4) A?, c = 19.547(4) A?, and β = 104.87(2)°. 5 crystallizes in the triclinic space group P1 with Z = 1, a = 8.916(2) A?, b = 11.177(7) A?, c = 12.009(4) A?, α = 81.15(5)°, β = 76.39(2)°, and γ = 67.47(3)°. Complex 13·0.5OEt2, crystallizes in the monoclinic space group P21/c with Z = 8, a = 21.840(5) A?, b = 17.664(6) A?, c = 36.890(7) A?, and β = 93.14(2)°.

Complexes of functional phosphines. 22. Cobalt(II) complexes with β-keto phosphines and corresponding cobalt(III) enolates. Crystal and molecular structures of the fac and mer isomers of [Co{Ph2PCH-...C(-...O)Ph}3]

Cobalt(II) complexes [CoX2{Ph2PCH2C(O)R}2] (1a, X = Cl, R = Ph; 1b, X = Cl, R = {(η-C5H4)Fe(η5-C5H 5)};; 2, X = Br, R = Ph; 3, X = I, R = Ph) containing keto phosphine ligands have been synthesized. The complexes react with base (NaH, NaOMe, K[OSiMe3]) in toluene or THF at 0°C to afford octahedral cobalt(III) enolates fac-[Co{Ph2PCH-...C(-...O)R}3] (5a, R = Ph; 5b, R = {η5-C5H4)Fe(η5-C 5H5)}) plus free ligand and inorganic products. Cobalt(II) intermediates are formed by the same reaction in methanol which precipitates the complexes formulated as [Co(μ-Cl){Ph2PCH-...C(-...O)R}{Ph 2PCH2C(O)R}]2 (4a, R = Ph; 4b, R = {(η5-C5H4)Fe(η5-C 5H5)}). The latter react in the presence of other solvents to give 5a,b. Disproportionation is proposed as the route to cobalt(III) enolates. 5a is formed as the kinetic product, and at higher reaction temperatures (ca. 100°C) 5a and the corresponding meridional isomer mer-[Co{Ph2PCH-...C(-...O)Ph}3] (6a) are produced in a 1:2 ratio. The solid-state structure of the fac and mer isomers 5a and 6a has been determined by single-crystal X-ray analysis. The toluene solvate of 5a crystallizes in the monoclinic space group P21/a with Z = 4 in a unit cell of dimensions a = 23.820(8) A?, b = 13.096(6) A?, c = 17.532(6) A?, and β = 97.98(2)°. 6a crystallizes in the monoclinic space group P21/n with Z = 4 in a unit cell of dimensions a = 13.592(8) A?, b = 21.175(6) A?, c = 16.930(6) A?, and β = 94.23(2)°. The structures have been solved and refined on the basis of 3110 (5a) and 3215 (6a) observed reflections to R and Rw values of 0.0575 and 0.0630 (5a) and 0.0323 and 0.0343 (6a), respectively.