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Our experiment was twofold: 1) Two different salen ligand derivatives were synthesized and complexed with Co(II) and Ni(II). Both ligands and ligand-metal complexes were characterized using various spectroscopic techniques, as well as ab initio computational techniques. The prepared catalysts were then used to oxidize selected phenols to corresponding quinones in a molecular oxygen rich environment. Data for salen catalysts with differing functional groups were compiled and used to determine possible reaction mechanisms for the catalytic conversion of various phenols to quinones. Catalytic efficiency was tracked using quantitative and spectroscopic techniques. 2) Proposed mechanisms were tested using several approaches, including the use of bare cobalt metal in oxidation tests, the synthesis of a Cu(II)-based catalyst, testing of catalyses in open air rather than in oxygen rich atmosphere, and time-controlled oxidations.
Background:
Organometallic salens are of interest because of their ability to coordinate with metals such that they form effective and highly selective catalytic complexes 1, 2, 3, 4. Organometallic salen ligands are very versatile in that their specific catalytic function and mechanism can be tuned by making changes to the structure of the ligand 5, 6, 7 . In addition, these structures can complex with a wide variety of transition metals, affording them even greater versatility. Some practical uses of these complexes include epoxide ring-opening catalysis 8, hetero Diels-Alder reactions 9, and hydrocyanations 10. They have also been explored in their Fig 1. Ligand 4b: Hydroxy substituted ability to help bind oxygen reversibly and in so doing, catalyze salen with benzyllic backbone. the oxidation of lignin 11. In our research group, we were interested in the catalytic ability of organometallic salens similar to 4b and 5a, pictured in figures 1 and 2, as facilitated through the binding of oxygen. All the ligands synthesized and tested were Schiff base ligands. The main structural variations employed were the synthesis of both an ethylene-based ligand backbone 5a, and Fig 1. Ligand 5a: Methyl substituted salen with ethylene backbone. an aromatic-based backbone 4b, and variation of the functional groups para- to the hydroxy groups on the imide aromatics. Compounds were synthesized as homogenously as possible. Nickel(II) and cobalt(II) were chosen to be our metal centers, as they would complex with similar geometries, yet differ in respect to their delectron count. It was believed that only the cobalt-Schiff base ligands would display catalytic activity, as they were able to catalyze oxygen activation because of their unpaired d-electron. This would allow for interaction with paramagnetic molecular oxygen, whereas nickel(II), with a filled dshell, would be unable to catalyze the oxidations of phenols by activating oxygen in this manner. In addition we explored the mechanism by which our cobalt-Schiff base ligands activate oxygen: structurally as described above, as well as by testing as many environmental variables as possible. These data are presented below, in the experimental section.
Experimental
Synthesis:
H HO O H2N H HN OH OH OH NH2
H OH H
NH2
OH NH2 H N O H HO OH2
Fig 2. Proposed mechanism for formation of ethylene-based Shiff base ligand 5a.
L5a (2,2'-((1E,1'E)-(ethane-1,2-diylbis(azanylylidene))bis(methanylylidene))bis(4methylphenol)): To a 100mL roundbottom flask containing 0.5446g (16mmol) 5methylsalicylaldehyde in 15 ml MeOH, 0.1136 mL (8 mmol) ethylenediamine was added directly via micropipet. The resulting solution was refluxed with stirring in a hot mineral oil bath for 90 minutes. The mixture was allowed to cool to room temperature and then immersed in an ice water bath. The precipitate was filtered by vacuum, and the filtrate discarded, yielding 0.5478g (85%) of fluffy, bright yellow-green, pearlescent, flaky crystals. NMR CDCL3 (ppm): 12.9 (2H, -OH), 8.3 (2H, imide), 6.97.1 (6H, aromatic), 3.29 (4H, -CH2), 2.3 (6H, -CH3). L4b (2,2'-((1E,1'E)-(1,2-phenylenebis(azanylylidene))bis(methanylylidene))bis(benzene1,4-diol)): To a 100mL roundbottom flask containing 0.5525g (16mmol) 5-hydroxysalicylaldehyde in 30mL MeOH, 0.2162g (8mmol) o-ethylenediamine dissolved in 15mL MeOH was added. The resulting solution was refluxed with stirring in a hot mineral oil bath for 150 minutes. The solution was allowed to cool to room temperature and then immersed in an ice water bath. Desired ligand precipitated out of solution, and vacuum filtration yielded 0.3469g (45%) very fine, shiny, bright-red powder. NMR CDCl3 (ppm): 12.1 (4H, -OH); 9.1 (2H, imide); 8.8; 7.5-6.8 (aromatic); 4.1 quartet; 3.2; 3.1, doublet. L5a Cobaltosalen: In a 150mL Erlenmeyer flask, 0.4500g (1.525 mmol) of ligand 5A was dissolved in 75mL of MeOH. The resulting solution was stirred with gentle heating, until the added ligand was completely dissolved. In a separate 150mL Erlenmeyer flask, 0.3798g (1.525 mmol) of Co(II) acetate was completely dissolved in a minimal amount of MeOH. The two solutions were combined, and allowed to stir without further heating for 10-15 minutes. The solution was removed and placed in an ice water bath, and the resulting precipitate was filtered by vacuum using fine fritted glass. The resulting solid was allowed to dry, yielding 0.6761g (81%) of very fine, black, fluffy, hair like material. ESI-MS: Single, prominent peak 353.2 m/z. Evans method NMR inconclusive.
L5a Nickelsalen: In a 150mL Erlenmeyer flask, 0.2501g (0.835 mmol) of ligand 5A was dissolved in 75mL of MeOH. The resulting solution was stirred with gentle heating, until the added ligand was completely dissolved. In a separate 150mL Erlenmeyer flask, 0.2099g (0.835 mmol) of Ni(II) acetate was completely dissolved in a minimal amount of MeOH. The two solutions were combined, and allowed to stir without further heating for 10-15 minutes. The solution was removed and placed in an ice water bath, and the resulting precipitate was filtered by vacuum using fine fritted glass. The resulting solid was allowed to dry, yielding 0.276g (60%) of fine, hair like, fluffy, brown material. NMR DMSO (ppm): 7.41 (2H, imide); 7.11-6.84 (aromatic); 3.44 (2H, -CH2); 2.23 (2H, -OH); 1.6. L4b Cobaltosalen: In a 150mL Erlenmeyer flask, 0.2347g (0.674 mmol) of ligand 5A was dissolved in 75mL of MeOH. The resulting solution was stirred with gentle heating, until the added ligand was completely dissolved. In a separate 150mL Erlenmeyer flask, 0.1680g (0.674 mmol) of Co(II) acetate was completely dissolved in a minimal amount of MeOH. The two solutions were combined, and allowed to stir without further heating for 10-15 minutes. The solution was removed and placed in an ice water bath, and the resulting precipitate was filtered by vacuum using fine fritted glass. The resulting solid was allowed to dry, yielding 0.1.732g (43%) of fine, black, powdery material. ESI-MS: Single, prominent peak 405.3 m/z. L4b Nickelsalen: In a 150mL Erlenmeyer flask, 0.4355g (1.25 mmol) of ligand 5A was dissolved in 75mL of MeOH. The resulting solution was stirred with gentle heating, until the added ligand was completely dissolved. In a separate 150mL Erlenmeyer flask, 0.3111g (1.25 mmol) of Ni(II) acetate was completely dissolved in a minimal amount of MeOH. The two solutions were combined, and allowed to stir without further heating for 10-15 minutes. The solution was removed and placed in an ice water bath, and the resulting precipitate was filtered by vacuum using fine fritted glass. The resulting solid was allowed to dry, yielding 0.4178g (56%) of extremely fine, powdery, red material. NMR CDCl3 (ppm): 8.41 (2H, imide); 7.45-6.85 (10H, aromatic); 5.35 (2H, -OH). L5a Coppersalen: In a 150mL Erlenmeyer flask, 0.2568g (0.844 mmol) of ligand 5A was dissolved in 75mL of MeOH. The resulting solution was stirred with gentle heating, until the added ligand was completely dissolved. In a separate 150mL Erlenmeyer flask, 0.1716g (0.844 mmol) of Cu(II) acetate was completely dissolved in a minimal amount of MeOH. The two solutions were combined, and allowed to stir without further heating for 10-15 minutes. The solution was removed and placed in an ice water bath, and the resulting precipitate was filtered by vacuum using fine fritted glass. The resulting solid was allowed to dry, yielding 0.2818g (66%) of hair like, fluffy, grey-black material. L4b Coppersalen: In a 150mL Erlenmeyer flask, 0.2591g (0.718 mmol) of ligand 5A was dissolved in 75mL of MeOH. The resulting solution was stirred with gentle heating, until the added ligand was completely dissolved. In a separate 150mL Erlenmeyer flask, 0.1557g (0.718 mmol) of Cu(II) acetate was completely dissolved in a minimal amount of MeOH. The two solutions were combined, and allowed to stir without further heating for 10-15 minutes. The solution was removed and placed in an ice water bath, and the resulting precipitate was filtered by vacuum using fine fritted glass. The resulting solid was allowed to dry, yielding 0.3031g (73%) of extremely fine, pearlescent, gold/brown material.
Initial Catalysis:
Initial catalytic oxidations of selected phenols were performed using a 10:1 substrate:catalyst molar ratio in 30mL MeOH, under constant molecular oxygen-rich atmosphere. L5a Nickelsalen + Phenol: To a 125mL Erlenmeyer flask containing 30mL methanol, 0.0935g (0.266 mmol) of ethylene-based nickel catalyst 5a was added with stirring. To the resulting solution, 0.2156g (2.66 mmol) phenol was added. NMR CDCl3 (ppm): 7.24 (H meta to OH); 6.93 (-H para to OH); 6.84 (-H ortho to OH); 5.35 (-OH). L5a Nickelsalen + Hydroquinone: To a 125mL Erlenmeyer flask containing 30mL methanol, 0.0799g (0.227 mmol) of ethylene-based nickel catalyst 5a was added with stirring. To the resulting solution, 0.2516g (2.27 mmol) hydroquinone was added. NMR DMSO (ppm): 8.59 (2H para OH); 6.57 (2H ortho to OH). L5a Nickelsalen + 2,6-dimethylphenol: To a 125mL Erlenmeyer flask containing 30mL methanol, 0.0721g (0.205 mmol) of ethylene-based nickel catalyst 5a was added with stirring. To the resulting solution, 0.2515g (2.05 mmol) 2,6-dimethylphenol was added. NMR CDCl3 (ppm): 6.93 (2H meta to CH3); 6.74 (-H para to OH); 4.66 (OH); 2.20 (6H on -CH3s). L5a Cobaltosalen + Phenol: To a 125mL Erlenmeyer flask containing 30mL methanol, 0.1003g (0.266 mmol) of ethylene-based cobalt catalyst 5a was added with stirring. To the resulting solution, 0.2550g (2.66 mmol) phenol was added. GC-MS: 3.38 min (68%), m/z: 108, 82 (-C2H2), 54 (-CO), 3.54min (32%), m/z: 94, 55 (-C4H7). NMR CDCl3 (ppm): 6.93 (2H meta to CH3); 6.80 (4H, ortho to OH); 6.74 (-H para to OH); 4.66 (OH); 2.20 (6H on -CH3s). L5a Cobaltosalen + Hydroquinone: To a 125mL Erlenmeyer flask containing 30mL methanol, 0.0802g (0.227 mmol) of ethylene-based cobalt catalyst 5a was added with stirring. To the resulting solution, 0.2518g (2.27 mmol) hydroquinone was added. GC-MS: 3.42 min (100%), m/z: 108, 82 (C2H2), 54 (-CO). NMR CDCl3 (ppm): 6.80 (4H, ortho to OH). L5a Cobaltosalen + 2,6-dimethylphenol: To a 125mL Erlenmeyer flask containing 30mL methanol, 0.0734g (0.205 mmol) of ethylene-based cobalt catalyst 5a was added with stirring. To the resulting solution, 0.2516g (2.05 mmol) 2,6-dimethylphenol was added. GC-MS: 5.36 min (46%), m/z: 122, 107 (-CH3), 91 (-O), 77 (-CH2); 5.51 min (54%), m/z: 122, 107 (CH3), 91 (-O), 77 (-CH4). L4b Nickelsalen + Phenol: To a 125mL Erlenmeyer flask containing 30mL methanol, 0.1143g (0.266 mmol) of benzene -based nickel catalyst 4b was added with stirring. To the resulting solution, 0.2542g (2.66 mmol) phenol was added. NMR CDCl3 : 7.24 (H meta to OH); 6.93 (-H para to OH); 6.84 (-H ortho to OH); 5.35 (-OH). L4b Nickelsalen + Hydroquinone: To a 125mL Erlenmeyer flask containing 30mL methanol, 0.0802g (0.227 mmol) of benzene -based nickel catalyst 4b was added with stirring. To the resulting solution, 0.2540g (2.27 mmol) hydroquinone was added. NMR DMSO (ppm): 8.59 (2H para OH); 6.57 (2H ortho to OH).
L4b Nickelsalen + 2,6-dimethylphenol: To a 125mL Erlenmeyer flask containing 30mL methanol, 0.0827g (0.205 mmol) of benzene-based nickel catalyst 4b was added with stirring. To the resulting solution, 0.2519g (2.05 mmol) 2,6-dimethylphenol was added. NMR CDCl3 (ppm): 6.93 (2H meta to CH3); 6.74 (-H para to OH); 4.66 (OH); 2.20 (6H on -CH3s). L4b Cobaltosalen + Phenol: To a 125mL Erlenmeyer flask containing 30mL methanol, 0.1102g (0.266 mmol) of benzene-based cobalt catalyst 4b was added with stirring. To the resulting solution, 0.2537g (2.66 mmol) phenol was added. GC-MS: 3.97 min (87%), m/z: 94, 66 (-C2H4, CO), 50 (-O); 5.68 min (11%), m/z: 113, 71 (-C2H2O), 57 (CH2); 6.19 min (2%), unknown substance. L4b Cobaltosalen + hydroquinone: To a 125mL Erlenmeyer flask containing 30mL methanol, 0.0904g (0.227 mmol) of benzene-based cobalt catalyst 4b was added with stirring. To the resulting solution, 0.2498g (2.27 mmol) hydroquinone was added. GC-MS: 3.28 min (94%), m/z: 108, 82 (C2H2), 54 (-CO); 6.95 min (6%), m/z: 138, 123 (-CH3), 108 (-CH3), 82 (-C2H2), 54(-CO). L4b Cobaltosalen + 2,6-dimethylphenol: To a 125mL Erlenmeyer flask containing 30mL methanol, 0.0857g (0.205 mmol) of benzene-based cobalt catalyst 4b was added with stirring. To the resulting solution, 0.2601g (2.05 mmol) 2,6-dimethylphenol was added. GC-MS: 5.54 min (100%), m/z: 136, 121 (-CH3), 108 (-CO), 79 (-CHO). In each of the above cases, the flasks were sealed using a standard rubber septum and copper wire, evacuated via respirator until the solution boiled, then flushed with pure, molecular oxygen. The solution was evacuated/flushed 3-5 times. After this, a constant oxygen-rich environment was obtained using a pressurized balloon. The solution was allowed to stir under constant oxygen pressure for 241 h. After the oxidation was complete, the solution was made into a slurry using celite media, and filtered by gravity through extra fine filter paper approximately one-third filled with silica gel, to facilitate removal of metal. Table 2 presents the experimental data for the first set of catalyses, and is discussed in further detail in the results and discussion section.
Open-Air Catalyses:
Once initial catalytic oxidation data had been gathered, the presence of pure, molecular oxygen was removed, and the oxidations were run in open air for comparable amounts of time (241 h), using only Co-based catalysts, as Ni had been shown to be ineffective. L5a Cobaltosalen + Phenol: To a 125mL Erlenmeyer flask containing 40mL methanol, 0.1090g (0.266 mmol) of ethylene-based cobalt catalyst 5a was added with stirring. To the resulting solution, 0.2758g (2.66 mmol) phenol was added. GC-MS: 3.71 min (100%) m/z: 94, 55 (-C4H7). NMR CDCl3 (ppm): 6.93 (2H meta to CH3); 6.74 (-H para to OH); 4.66 (OH); 2.20 (6H on -CH3s). L5a Cobaltosalen + Hydroquinone: To a 125mL Erlenmeyer flask containing 40mL methanol, 0.0986g (0.227 mmol) of ethylene-based cobalt catalyst 5a was added with stirring. To the resulting solution, 0.2538g (2.27 mmol) hydroquinone was added. GC-MS: 3.23 min (61%), m/z: 94, 55 (C4H7); 6.31 min (35%), m/z: 138, 123 (-CH3), 108 (-CH3), 95, 82 (-C2H2), 69, 54 (-CO); 8.81 min (5%), m/z: 138, 122, 110, 95, 82, 69.
L5a Cobaltosalen + 2,6-dimethylphenol: To a 125mL Erlenmeyer flask containing 40mL methanol, 0.0910g (0.205 mmol) of ethylene-based cobalt catalyst 5a was added with stirring. To the resulting solution, 0.2561g (2.05 mmol) 2,6-dimethylphenol was added. GC-MS: 5.03 min (70%), m/z: 122, 107 (-CH3), 91 (-O), 77 (-CH2); 5.14 min (15%), m/z: 136, 108 (-C2H4), 96, 79 (-CHO), 68; 10.68 min (15%), m/z: 242, 227, 211, 196, 184, 169, 152, 141, 121, 98, 91, 82, 77, 69, 63, 51. L4b Cobaltosalen + Phenol: To a 125mL Erlenmeyer flask containing 40mL methanol, 0.1102g (0.266 mmol) of benzene-based cobalt catalyst 4b was added with stirring. To the resulting solution, 0.2537g (2.66 mmol) phenol was added. GC-MS: 5.68 min (100%) m/z: 94, 55 (-C4H7). NMR CDCl3 (ppm): 6.93 (2H meta to CH3); 6.74 (-H para to OH); 4.66 (OH); 2.20 (6H on -CH3s). L4b Cobaltosalen + Hydroquinone: To a 125mL Erlenmeyer flask containing 40mL methanol, 0.0986g (0.227 mmol) of benzene-based cobalt catalyst 4b was added with stirring. To the resulting solution, 0.2538g (2.27 mmol) hydroquinone was added. GC-MS: 3.23 min (91%), m/z: 94, 55 (C4H7); 6.29 min (9%), m/z: 108, 82 (-C2H2), 54 (-CO). NMR CDCl3 (ppm): 6.93 (2H meta to CH3); 6.74 (-H para to OH); 4.66 (OH); 2.20 (6H on -CH3s). L4b Cobaltosalen + 2,6-dimethylphenol: To a 125mL Erlenmeyer flask containing 40mL methanol, 0.0910g (0.205 mmol) of benzene-based cobalt catalyst 4b was added with stirring. To the resulting solution, 0.2561g (2.05 mmol) 2,6-dimethylphenol was added. GC-MS: 3.23 min (21%), m/z: 94, 55 (-C4H7); 6.29 min (79%), m/z: 108, 82 (-C2H2), 54 (-CO). NMR CDCl3 (ppm): 6.93 (2H meta to CH3); 6.74 (-H para to OH); 4.66 (OH); 2.20 (6H on -CH3s). In each of the above cases, the solution was allowed to stir in an open Erlenmeyer flask under normal atmospheric conditions (~1 atm, ~20C, humidity unknown, ~195 ft. elevation) for 241 h. After the oxidation was complete, the solution was made into a slurry using celite media, and filtered by gravity through extra fine filter paper approximately one-third filled with silica gel, to facilitate removal of metal. Results are presented in Table 3.
Acetate Catalysis:
In addition, the catalytic ability of bare Co(II) acetate was tested both with and without the presence of pure, molecular oxygen.
Open Air:
Cobalt (II) Acetate + Phenol: To a 125mL Erlenmeyer flask containing 40mL methanol, 0.0672g (0.266 mmol) of cobalt (II) acetate was added with stirring. To the resulting solution, 0.2610g (2.66 mmol) phenol was added. GC-MS: 3.69 min (100%), m/z: 108, 82 (-C2H2), 54 (-CO). NMR CDCl3 : 7.24 (H meta to OH); 6.93 (-H para to OH); 6.84 (-H ortho to OH); 5.35 (-OH). Cobalt (II) Acetate + Hydroquinone: To a 125mL Erlenmeyer flask containing 40mL methanol, 0.0986g (0.227 mmol) of cobalt (II) acetate was added with stirring. To the resulting solution, 0.2538g (2.27 mmol) hydroquinone was added. GC-MS: 3.21 min (1%), m/z: 108, 82 (-C2H2), 54 (CO); 6.52 min (99%), m/z: 138, 123 (-CH3), 108 (-CH3), 82 (-C2H2), 54(-CO). 6
Cobalt (II) Acetate + 2,6-dimethylphenol: To a 125mL Erlenmeyer flask containing 40mL methanol, 0.0910g (0.205 mmol) of cobalt (II) acetate was added with stirring. To the resulting solution, 0.2561g (2.05 mmol) 2,6-dimethylphenol was added. GC-MS: 5.03 min (100%), m/z: 122, 107 (-CH3), 91 (-O), 77 (-CH2). NMR CDCl3 (ppm): 6.93 (2H meta to CH3); 6.74 (-H para to OH); 4.66 (OH); 2.20 (6H on -CH3s). In each of the above cases, the solution was allowed to stir in an open Erlenmeyer flask under normal atmospheric conditions (~1 atm, ~20C, humidity unknown, ~195 ft. elevation) for 241 h. After the oxidation was complete, the solution was made into a slurry using celite media, and filtered by gravity through extra fine filter paper approximately one-third filled with silica gel, to facilitate removal of metal.
Oxygen:
Cobalt (II) Acetate + Phenol: To a 125mL Erlenmeyer flask containing 40mL methanol, 0.0716g (0.266 mmol) of cobalt (II) acetate was added with stirring. To the resulting solution, 0.2512g (2.66 mmol) phenol was added. GC-MS: 3.69 min (100%), m/z: 108, 82 (-C2H2), 54 (-CO). NMR CDCl3 : 7.24 (H meta to OH); 6.93 (-H para to OH); 6.84 (-H ortho to OH); 5.35 (-OH). Cobalt (II) Acetate + Hydroquinone: To a 125mL Erlenmeyer flask containing 40mL methanol, 0.0791g (0.227 mmol) of cobalt (II) acetate was added with stirring. To the resulting solution, 0.2573g (2.27 mmol) hydroquinone was added. GC-MS: 3.21 min (5%), m/z: 108, 82 (-C2H2), 54 (CO); 6.52 min (95%), m/z: 138, 123 (-CH3), 108 (-CH3), 82 (-C2H2), 54(-CO). NMR CDCl3 (ppm): 6.93 (2H meta to CH3); 6.74 (-H para to OH); 4.66 (OH); 2.20 (6H on -CH3s). Cobalt (II) Acetate + 2,6-dimethylphenol: To a 125mL Erlenmeyer flask containing 40mL methanol, 0.0780g (0.205 mmol) of cobalt (II) acetate was added with stirring. To the resulting solution, 0.2576g (2.05 mmol) 2,6-dimethylphenol was added. GC-MS: 5.03 min (100%), m/z: 122, 107 (-CH3), 91 (-O), 77 (-CH2). NMR CDCl3 (ppm): 6.93 (2H meta to CH3); 6.74 (-H para to OH); 4.66 (OH); 2.20 (6H on -CH3s). In each of the above cases, the flasks were sealed using a standard rubber septum and copper wire, evacuated via respirator until the solution boiled, then flushed with pure, molecular oxygen. The solution was evacuated/flushed 3-5 times. After this, a constant oxygen-rich environment was obtained using a pressurized balloon. The solution was allowed to stir under constant oxygen pressure for 241 h. After the oxidation was complete, the solution was made into a slurry using celite media, and filtered by gravity through extra fine filter paper approximately one-third filled with silica gel, to facilitate removal of metal. Results are presented in Table 4.
Cooperative Data:
Table 5 gives all data available for the entire research group, for oxidations performed with variously substituted Ni- and Co-based catalysts, performed in oxygen rich environments. Efforts were made to use homogenous experimental technique and maintain a catalysis time of 241 h.
obtained using a pressurized balloon. The solution was allowed to stir under constant oxygen pressure for 241 h. After the oxidation was complete, the solution was made into a slurry using celite media, and filtered by gravity through extra fine filter paper approximately one-third filled with silica gel, to facilitate removal of metal. Results are presented in Table 6.
Job$Number Job$Name 14117 Elthylenediamine 14123 5Hmethylsalicylaldehyde 14181 2,5Hdihydroxybenzaldehyde 14182 OHphenylenediamine 14172 L5A$+$Ni 14291 L5A$+$Co 14375 L4B$+$Co 14392 L4B$+$Ni 14493 L4B$+$Ni$H$MeOH 14495 L4B$+$Ni$H$MeOH 14506 L4B$+$Ni$H$MeOH$H$Lv$3$GEOM 14513 L4B$+$Co$H$MeOH 14205 L4B 14150 L5A L5A$MeOH L4B$MeOH
Stoichiometry C2H8N2 C8H8O2 C7H6O3 C6H8N2 C18H18N2NiO2 C18H18CoN2O2(2) C20H14CoN2O4(2) C20H14N2NiO4 C20H14N2NiO4 C20H14N2NiO4 C20H14N2NiO4 C20H14CoN2O4(2) C20H16N2O3 C18H20N2O2
Basis 6H311+G(d,p) 6H311+G(d,p) 6H311+G(d,p) 6H311+G(d,p) 6H311+G(d,p) 6H311+G(d,p) 6H311+G(d,p) 6H311+G(d,p) 6H311+G(d,p) 6H311+G(d,p) 6H311+G(d,p) 6H311+G(d,p) 6H311+G(d,p) 6H311+G(d,p)
B3LYP$E$(Hartree) B3LYP$E(kcal/mol) H190.5868869 H119594.9868 H460.2423812 H288806.2364 H496.1586508 H311344.0188 H343.0636463 H215275.5256 H2465.373344 H1547043.962 H2339.83088 H1468264.936 H2564.131102 H1609015.344 H2689.675866 H1687795.813 H2689.723229 H1687825.534 H2689.723222 H1687825.529 H3192.68593 H2003439.156 H2564.178405 H1609045.027 H1107.238567 H694802.1657 H958.1811793 H601267.3137 H958.2004969 H601279.4356 H1182.4817 H742017.9091
78779.02594 78780.46916
E$for$ethylene/CH3/Co$resulting$from$MeOH$calculations$vs$gas$phase: E$for$bare$ethylene/CH3$resulting$from$MeOH$calculations$vs$gas$phase:
29.7211543 12.12196723
kcal/mol kcal/mol
metal' Ni' Co' Ni' Co' Ni' Co' Ni' Co' Ni' Co' Ni' Co'
substrate'(g)' catalyst'(g)' 0.2516' 0.0935' 0.2550' 0.2542' 0.2537' 0.5216' 0.2518' 0.2534' 0.2497' 0.2515' 0.2516' 0.2519' 0.2601' 0.1003' 0.1143' 0.1102' 0.0799' 0.0802' 0.0822' 0.0904' 0.0721' 0.0734' 0.0827' 0.0857'
oxidation'(%)a'
0' 68' 0' 88' 0' 100' 0' 100' 0' 53' 0' 100'
lease'note'that'all'NiHbased'catalyses'were'characterized'via'NMR'spectroscopy'only,'whereas'CoHbased'oxidation'ratios'were'obtained' solely'through'GCHMS.' ' ' # Table 3. Experimental data for Co-based catalyses performed in open air.
metal'
substrate'(g)' catalyst'(g)' 0.2758' 0.1090' 0.2512' 0.0716' 0.0986' 0.0791' 0.0910' 0.0780' 0.2538' 0.2573' 0.2561' 0.2576'
oxidation'(%)a'
0' 0' 61a' 90a' 15b' 21'
Co'
ossible'intermediate'formed,'no'substrate'remained.'interestingly,'70%'substrate'remained,'while'14%'appeared'to'have' polymerized.'
Table 4. Experimental data for testing of catalytic ability in bare Co(II) Acetate.
''
open'air' oxygen' open'air' oxygen' open'air' oxygen'
catalyst'
Co(II)'Acetate'
substrate'(g)' catalyst'(g)' 0.2610' 0.0672' 0.2695' 0.0700' 0.2523' 0.0596' 0.2596' 0.0696' 0.2551' 0.0541' 0.2636' 0.0597'
oxidation'(%)a'
0' 0' 1' 5' 0' 0'
10
Nickel' hydro/ethylene+ chloro/ethylene+ methyl/ethylene+ hydroxy/ethylene+ hydro/diaminobenzene+ chloro/diaminobenzene+ methyl/diaminobenzene+ hydroxy/diaminobenzene+ Cobalt' hydro/ethylene+ chloro/ethylene+ methyl/ethylene+ hydroxy/ethylene+ hydro/diaminobenzene+ chloro/diaminobenzene+ methyl/diaminobenzene+ hydroxy/diaminobenzene+ + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + +
'
Phenol' Hydroquinone' 2,65DMP' Substrate' Oxidized' Substrate' Oxidized' Substrate' Oxidized' 100+ 0+ 100+ 0+ 100+ 0+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 99.6+ 100+ 100+ 100+ 100+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0.1+ 0+ 0+ 0+ 0+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+
'
***+ ***+ ***+ ***+ ***+ ***+ Phenol' Hydroquinone' 2,65DMP' Substrate' Oxidized' Substrate' Oxidized' Substrate' Oxidized' 100+ 0+ 48+ 42+ 35+ 65+ 100+ 100+ 100+ 100+ 32+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 100+ 12+ ***+ 0+ 0+ 0+ 0+ 68+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 88+ ***+ 94+ 5+ ***+ 0+ 0+ 100+ ***+ ***+ 100+ 88+ 90+ 70+ 0+ 0+ ***+ 6+ 95+ ***+ 100+ 100+ 0+ ***+ ***+ 0+ 12+ 10+ 30+ 100+ 100+ ***+ 18+ 100+ 18+ 51+ 47+ 6+ 72+ 5+ 1+ 76+ 76+ 20+ 0+ 0+ 0+ 82+ 0+ 82+ 49+ 53+ 94+ 28+ 95+ 99+ 24+ 24+ 80+ 100+ 100+ 80+
11
Table 6. Experimental data for Cu-based catalyses performed under constant pressure oxygen.
metal'
substrate'(g)' catalyst'(g)' 0.1865' 0.0654' 0.2475' 0.1007' 0.0667' 0.1004' 0.0684' 0.1029' 0.2069' 0.2685' 0.2274' 0.3013'
oxidation'(%)a'
0' 0' 0' 0' 0' 0'
Cu'
Computational Work:
Density functional theory and semi-empirical self-consistent field methods were used to model the various reactants, ligand products, and metallated complexes. The typical approach was to build a structure and apply increasingly robust theory and basis set optimizations. Geometry optimizations were carried out beginning with RHF/STO-G and culminating with B3LYP/6-311G*(d,f), incrementing the theory/basis sets to higher levels slowly, so as to optimize computational cost. Following this, vibrational frequencies and NMR spectra were predicted using B3LYP/6-311G*(d,f). The optimized ligand structures were then metallated, using nickel and cobalt, and
Fig 5. Structure of methyl-substituted L5A, calculated at
12
optimized with increasingly robust theory/basis sets, as described above. Ground state energies for the different ligands in gas phase were compared to the ground state energies for the metallated ligands in gas phase. At this point, the calculations were then repeated in methanol solvent, as this was our primary experimental solvent. Given adequate time, one could use bomb calorimetry and IR spectroscopy to compare the theoretically calculated values for some of these compounds to those obtained experimentally.
Fig 6. Structure of hydroxy-substituted L4b, The resulting structure for methyl-substituted L5a calculated at B3LYP/6-311G*(d,f) was slightly non-planar, due to the free rotation of the C-N bonds attached to the ethylene backbone. Interestingly, the structure for bare benzosalen 5b was distinctly non-planar, with the free rotation of the imide functional groups resulting in two different low-energy geometry optimizations, as pictured in figures 4 and 5. The energy difference between the two salens in gas and solvent phase is shown in table 1. The optimized structuresa were then metallated with nickel or cobalt, then further optimized as described above, until geometries and energies were obtained at the B3LYP/6-311G*(d,p) level. The process was again repeated both with and without methanol solvation, in order to help evaluate the importance of methanol in stabilizing the ground state structures. Following the addition of the metal centers, the energies for the two structures differed by a margin of about 29 kcal/mol, as shown in table 1. This not insignificant number suggests that the choice of solvent possibly plays an Fig 7. Alternate structure of hydroxy-substituted L4b, important role in the structure and by extension, the calculated at BP86/6-311G*(d,p) function of these catalysts. Additional computational work was done with respect to the cobaltosalen ligands, as these displayed catalytic activity, whereas the nickel(II) based salens did not. Specifically, because the cobalt compounds had a single unpaired electron, ROHF and UHF geometry and energy optimizations were performed on the ethylene-based ligand 5a, complexed with cobalt(II). The results of these calculations are displayed in figure 9, with energy comparisons shown in table 1. As shown in figure 9, the structure Fig 8. Structure for cobaltosalen L5a, resulting from B3LYP/6-311G*(d,p) resulting from unrestricted Hartreegeometry optimization in Gaussian 03.
13
Fockb calculations displayed a slightly different geometry minimum, in which the metal appears to have coordinated in a very square planar configuration. This is slightly different from the results obtained using restricted degenerate-orbital calculations at a much higher level of theory and basis set pictured in figure 8, in which the metal center is slightly distorted from being planar. As seen in figure 10, the flexibility of the ligand backbone is lost with the addition of the metal center. The cobalt-Schiff base salen adopts an extremely planar energy minimum, allowing much better steric access for trans ligands to coordinate to the metal center. This is a possible issue, as seen in figure 11, where a possible superoxide
Fig 9. Structure for cobaltosalen L5a, resulting from unrestricted B3LYP/631G+(d) geometry optimization in Firefly.
Fig 11. Transition state superoxide structure for cobaltosalen L5a, resulting from BP86/6-31G(d) transition state search in Gaussian 03.
b
transition state has been modeled. The ethylene backbone lends a certain flexibility to the complex, allowing it to twist slightly out of an octahedral conformation about the metal center. However, it is difficult to say whether the additional flexibility allows for a lower energy conformation to be achieved, as there was insufficient time to model the L5a superoxide transition state. One could Fig 10. Structure for cobaltosalen L4b, resulting from B3LYP/6-311G*(d,p) compare the ground state energies of the geometry optimization in Gaussian 03. cobalt-Schiff base catalysts with the transition state energies of the superoxide complexes. The resulting energy delta could be indicative as to whether the additional flexibility of the ethylene backbone is energetically favorable versus the rigid planarity of the aromatic backbone. In the case of L4b, the metal center is naturally in an extremely planar configuration, whereas in L5a, the square planar configuration of the metal center was achieved only through a propeller-like twisting of the ligand backbone. Further computational work could resolve much of this, but the high computational cost would necessitate an extended period of study.
Firefly (PC GAMESS) version 7.1.G, build number 5620: $BASIS GBASIS=N31 NGAUSS=6 NDFUNC=1 $CONTRL SCFTYP=UHF RUNTYP=OPTIMIZE DFTTYP=B3LYP MULT=2 NOSYM=1 MAXIT=300 $SYSTEM MWORDS=150 KDIAG=-2 $SCF DIRSCF=.T. FDIFF=.T. $STATPT OPTTOL=0.0001 NSTEP=50 HESS=CALC $FORCE METHOD=NUMERIC $END
14
It should be noted that though some catalytic activity was reported for nickel-Schiff base ligand catalyses, this was likely due to autooxidation of hydroquinone in the presence of excess oxygen, as will be discussed later in the experimental. d ~1 atm, ~20C, humidity unknown, ~195 ft. elevation
15
L5a and 90% for L4b. Midway between the two was 2,6-dimethylphenol, which dropped from 53% for L5a and 100% for L4b in oxygen, to 16% and 21%, respectively. This suggests that an important part of the oxygen-activated catalytic mechanism possibly occurs at the hydroxy site, as hydroquinone has 2:1 as compared with phenol and 2,6-dimethylphenol. The presence of oxygen also increased the catalytic activity of bare cobalt(II) acetate, as discussed below. Table 4 presents data obtained for oxidations performed with bare Co(II) acetate, both with and without the presence of pure, molecular oxygen. This was done in order to both reinforce the importance of an oxygen rich catalytic environment, and to compare the catalytic ability of bare metal to that of our ligated metal catalysts. Interestingly, some oxidation was indeed observed, though only in hydroquinone. Oxidations run in normal atmospheric conditionsd yielded about 1% conversion from hydroquinone to quinone, whereas oxidations run in an oxygen rich environment yielded about 5%. This suggests that the salen ligands play a critical role in activating the metal center for oxygen catalysis. This also suggests that the hydroxy groups on the phenols are important in the oxidation mechanism, again since hydroquinone has 2:1 versus the other phenols investigated. Table 6 presents data obtained for oxidations performed with copper(II)-based catalysts, complexed with L5a and L4b. Copper-Schiff base ligands were chosen for testing, as they would have an unpaired d-electron, similar to that in Co(II), and could conceivably exhibit similar catalytic activity. Oxidations performed with Cu-based salen catalysts suggest that an unpaired outer electron plays an important role in oxidation catalysis, but that it is not the only factor in determining catalytic activity. While Cu(II) does in deed have an unpaired d-electron, it displayed zero catalytic activity. This suggests that geometry and crystal field stabilization also play a critical role in oxygen activation for catalysis of oxidations. Because Cu(II) is d9, it will likely be energetically favorable to adopt a square planar configuration when coordinating with a salen ligand, but not energetically favorable to interact with oxygen. This is possibly a result of energy separation between the dxy and dx2-y2 orbitals. Cu(II) complexes could be more stable in square planar, whereas Co(II) complexes are more stable in octahedral configuration. Computational results could help to answer these questions, especially if used in OMe OMe OMe conjunction with R N N N N N N N N UV-Vis O2 Co Co Co Co experimental, in O O O O O O O O O O O order to explore O O the energy gaps H between the dorbitals. Figure OMe 13 outlines a O O N O N OMe R Co possible N N O O + Co mechanism for O O O the oxidation of O R O R R O phenols by OH cobalt-Schiff OMe base catalysts, O O O N N as seen in our MeOH Co experimental. O O
O O R O O O R HO O R H2O R
Fig 13. Proposed catalytic mechanism for cobalt-Schiff base oxidation of phenols to quinones.
16
Works Cited
1. Zhang, W.; Loebach, J.; Wilson, S.; Jacobsen, E. Enantioselective Epoxidation of Unfunctionalized Olefins Catalyzed by Salen Manganese Complexes. J. Am. Chem. 1009, 112, 2801-2803. 2. Jacobsen, E.; Zhang, W.; Muci, A.; Ecker, J.; Deng, L. Enantioselective Epoxidation Catalysts Derived from 1,2-Diaminocyclohexane. J. Am Chem. 1991, 113, 7063-7064. 3. Groves, J.; Nemo, T. Epoxidation Reactions Catalyzed by Iron Porphyrins - Oxygen Transfer from Iodsylbenzene. J. Am. Chem. Soc. 1983, 105 (18), 5786-5791. 4. Caputo, C.; Jones, N. Developments in Asymmetric Catalysis by Chiral Chelating NitrogenDonor Ligands. Dalton Transactions 2007, 41 (41), 4627-4640. 5. Schaus, S.; Brandes, B.; Larrow, J.F.; Tokunaga, M.; Hansen, K.; Gould, A.; Furrow, M.; Jacobsen, E. Highly Selective Hydrolytic Kinetic Resolution of Terminal Epoxides Catalyzed by Chiral Salen-Co(III) Complexes. Practical Synthesis of Enantioenriched Terminal Epoxides and 1,2-Diols. JACS Articles. 2001, 124 (7), 1307-1315. 6. Yu, X.; Huang, J.; Yu, W.; Che, C. Polymer-Supported Ruthenium Porphyrins: Versatile and Robust Epoxidation Catalysts with Unusual Selectivity. J. Am. Chem. Soc. 2000, 122 (22), 53375342. 7. Brandes, B.; Jacobsen, E. Highly Enantioselective, Catalytic Epoxidation of Trisubstituted Olefins. J. Org. Chem. 1994, 59, 4378-4380. 8. Wu, M.; Jacobsen, E. Asymmetric Ring Opening of Meso Epoxides with Thiols:! Enantiomeric Enrichment Using a Bifunctional Nucleophile. J. Org. Chem. 1998, 63 (15), 5252-5255. 9. Schaus, S.; Brnalt, J.; Jacobsen, E. Asymmetric Hetero-DielsAlder Reactions Catalyzed by Chiral (Salen)Chromium(III) Complexes. J. Org. Chem. 1998, 63 (2), 403-406. 10. Belokon, Y.; North, M.; Parsons, T. Vanadium-Catalyzed Asymmetric Cyanohydrin Synthesis. Org. Lett 2000, 2 (11), 1617-1620. 11. Zhou, X.; Liu, J. Co(salen) catalysed oxidation of synthetic lignin-like polymer: Co(salen) effects; Paper; Kunming University of Science and Technology: Guangzhou China, 2012.
17
Appendix!
! !
Fig$2.$Computationally!predicted!NMR!spectrum!of!2,59dihydroxybenzaldehyde.!Gaussian!03!9!B3LYP/69311G*(d,p)$
Fig$1.!Computationally!predicted!NMR!spectrum!of!59methylsalicyaldehyde.!Gaussian!03!9!B3LYP/69311G*(d,p)$
! ! ! ! !
Fig$3.$Computationally!predicted!NMR!spectrum!of!ethylenediamine.!Gaussian!03!9!B3LYP/69311G*(d,p)$
Fig$4.$Computationally!predicted!NMR!spectrum!of!2,59dihydroxybenzaldehyde.!Gaussian!03!9!B3LYP/69311G*(d,p)$ $
Fig$5.$Computationally!predicted!NMR!spectrum!of!ethylene/methyl!L5a.!Gaussian!03!9!B3LYP/69311G*(d,p)$ $
Fig$6.$Computationally!predicted!IR!spectrum!of!L5a.!Gaussian!03!9!B3LYP/69311G*(d,p)$
Fig$7.$Computationally!predicted!IR!spectrum!of!2,59dihydroxybenzaldehyde.!Gaussian!03!9!B3LYP/69311G*(d,p)$
Fig$8.!Computationally!predicted!IR!spectrum!of!o9phenylenediamine.!Gaussian!03!9!B3LYP/69311G*(d,p)!
Fig$9.$Computationally!predicted!IR!spectrum!of!L4a!+!Co(II).!Gaussian!03!9!B3LYP/69311G*(d,p)$
Fig$10.$Computationally!predicted!IR!spectrum!of!L4b!+!Co!(II).!Gaussian!03!9!B3LYP/69311G*(d,p)$
t-buOH OH (Hz) 1246.64 1239.02 1231.4 1224.07 D corrected (g/cm^3) 1.10845 1.10395 1.09945 1.09495
Mass Susceptibility DMSO [Co] complex -0.00000773 20 0.35328 kg/mol Mm (Co) complex NA= 6.022E+23 Uo= 0.000001256 k= 1.38E-23
6.35E&09(
y"="2E&06x"+"1E&09" R"="0.97064"
6.3E&09(
X"(kg/mol)""
6.25E&09(
6.2E&09(
6.15E&09(
6.1E&09(
6.05E&09( 0.00318(
0.0032(
0.00322(
0.00324(
0.00326( 1/T(K)""
0.00328(
0.0033(
0.00332(
0.00334(
0.00336(