KR101814077B1 - Nickel peroxo complex, active oxygen carrier and a method for control of the nucleophilic oxidative reaction rate comprising the same - Google Patents
Nickel peroxo complex, active oxygen carrier and a method for control of the nucleophilic oxidative reaction rate comprising the same Download PDFInfo
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- KR101814077B1 KR101814077B1 KR1020160002704A KR20160002704A KR101814077B1 KR 101814077 B1 KR101814077 B1 KR 101814077B1 KR 1020160002704 A KR1020160002704 A KR 1020160002704A KR 20160002704 A KR20160002704 A KR 20160002704A KR 101814077 B1 KR101814077 B1 KR 101814077B1
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- reaction rate
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 300
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 60
- 230000000269 nucleophilic effect Effects 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000001301 oxygen Substances 0.000 title abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 15
- 230000001590 oxidative effect Effects 0.000 title description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 8
- 238000010520 demethylation reaction Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000017858 demethylation Effects 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 34
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 102000004190 Enzymes Human genes 0.000 abstract description 9
- 108090000790 Enzymes Proteins 0.000 abstract description 9
- -1 nickel peroxide Chemical class 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 8
- 230000036983 biotransformation Effects 0.000 abstract description 6
- 230000004060 metabolic process Effects 0.000 abstract 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 150000001299 aldehydes Chemical class 0.000 description 15
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 14
- 238000003775 Density Functional Theory Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 230000009257 reactivity Effects 0.000 description 11
- 238000001237 Raman spectrum Methods 0.000 description 10
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 10
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 10
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 230000004783 oxidative metabolism Effects 0.000 description 6
- 230000010627 oxidative phosphorylation Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910020366 ClO 4 Inorganic materials 0.000 description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 5
- 229910018553 Ni—O Inorganic materials 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- JDRCAGKFDGHRNQ-UHFFFAOYSA-N nickel(3+) Chemical compound [Ni+3] JDRCAGKFDGHRNQ-UHFFFAOYSA-N 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 4
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
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- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 150000002500 ions Chemical class 0.000 description 3
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- 239000011159 matrix material Substances 0.000 description 3
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- IQVAERDLDAZARL-UHFFFAOYSA-N 2-phenylpropanal Chemical compound O=CC(C)C1=CC=CC=C1 IQVAERDLDAZARL-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000003592 biomimetic effect Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- STYFDKOQURBOGQ-UHFFFAOYSA-N 1,4,7,10-tetramethyl-1,4,7,10-tetrazacyclododecane Chemical compound CN1CCN(C)CCN(C)CCN(C)CC1 STYFDKOQURBOGQ-UHFFFAOYSA-N 0.000 description 1
- XZYQXHKQLPUZEO-UHFFFAOYSA-N 1,4,7,10-tetramethyl-1,4,7,10-tetrazacyclotridecane Chemical compound CN1CCCN(C)CCN(C)CCN(C)CC1 XZYQXHKQLPUZEO-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 102000016938 Catalase Human genes 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 102000018832 Cytochromes Human genes 0.000 description 1
- 108010052832 Cytochromes Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 206010027476 Metastases Diseases 0.000 description 1
- PHXQIAWFIIMOKG-UHFFFAOYSA-N NClO Chemical compound NClO PHXQIAWFIIMOKG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 108010063734 Oxalate oxidase Proteins 0.000 description 1
- 101000695243 Rhodococcus jostii (strain RHA1) Biphenyl 2,3-dioxygenase subunit alpha Proteins 0.000 description 1
- 102000019197 Superoxide Dismutase Human genes 0.000 description 1
- 108010012715 Superoxide dismutase Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001826 continuous-wave electron spin resonance spectroscopy Methods 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- XYNZKHQSHVOGHB-UHFFFAOYSA-N copper(3+) Chemical compound [Cu+3] XYNZKHQSHVOGHB-UHFFFAOYSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
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- 239000003643 water by type Substances 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/14—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The present invention relates to a nickel peroxo complex, an active oxygen carrier comprising the nickel peroxide complex, and a nucleophilic oxidation reaction rate control method comprising the same, wherein the nickel peroxo complex according to the present invention stably incorporates O 2 as a sido- And by controlling the steric hindrance of the substituent of the supporting ligand, the reaction rate can be easily controlled in the nucleophilic oxidation reaction. Therefore, it is possible to control the reaction rate by various means including the biotransformation of naturally occurring molecules that activate O 2 , the oxidation metabolism of the living body, It can be usefully used as a mimetic substance of a metal enzyme or a biomolecule having a desired reaction rate in a biological reaction.
Description
The present invention relates to a nickel peroxo complex, an active oxygen carrier containing the same, and a nucleophilic oxidation reaction rate control method comprising the same.
The metal enzyme activates O 2 to perform a variety of biological reactions including the biotransformation of naturally occurring molecules, the oxidative metabolism of the biomass, and oxidative phosphorylation. In addition, one of the purposes of biomimetic research is to understand the detailed mechanism of O 2 activation and oxygenation reaction and the structure of reactive intermediates formed at active sites of metal enzymes. In the overall mechanism of O 2 activation, O 2 first binds to the center of the reduced metal to form a metal-superoxo or metal-peroxo intermediate. High-valent metal-oxo species are then produced, which are believed to carry out the oxidation of the substrate as the oxygen-oxygen bond breaks. Among the metal-oxygen intermediates, mononuclear metal-O 2 additions, such as metal-superoxo or -peroxo species, have been found in O 2 activation cycles by metal enzymes including heam or non-heme metals It has attracted attention as a core intermediate.
In biomimetic and synthetic chemistry, synthesis of mononuclear metal-O 2 complexes including titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and transition metals in two or three cycles has been synthesized and various spectroscopic techniques and X- , And their reactivity has been extensively studied.
For example, Mn (Ⅲ) peroxo intermediates have been used as important active species in manganese-containing enzymes including oxalate oxidase, catalase, and superoxide dismutase. Mononuclear Fe (Ⅲ) (Eg, cytochromes P450 and Rieske dioxygenases).
Further, as the mononuclear Fe (III) peroxo species, an Fe (III) peroxo complex such as [Fe III (TMC) (O 2 )] + is converted completely into Fe (III) hydroperoxo complex , And it has been studied that OO bonds are easily separated to form an Fe (IV) oxo complex (see Non-Patent Document 1).
Further, studies on mononuclear Cu (III) peroxo complexes have shown that side-on (η 2) and end-on (η 1) copper (II) -peroxo and sidone (η 2) to find out the X- ray crystal structure of the complex, O 2 in the form of coordination (e.g., a side-on vs end-on bonding) and electronic characteristics of the copper core 2 -O (for example, copper (ⅱ) - Super-oxo vs Copper (III) -peroxo) has been studied to vary depending on the supporting ligand of the copper complex (Non-Patent Document 2).
In addition, the analysis and reactivity of end-on nickel (II) superoxo complexes having a side-on nickel (III) peroxo complex with a macrocyclic ligand of 12 atoms and a macrocyclic ligand of 14 atoms have been studied (See Patent Document 1). This document describes that a complex having a macrocyclic ligand of 12 atoms exhibits nucleophilic reactivity with respect to an organic material, while a complex having a macrocycle ligand of 14 atoms shows electrophilic reactivity with an organic material.
As described above, the mononuclear metal-O 2 complex exhibits nucleophilic reactivity in the reaction such as aldehyde demethylation. However, in order to control the rate of this reaction, it is necessary to change the ring size of the ligand or to convert the active oxygen to peroxo, , Superoxo, and the like.
Thus, in the present inventors to enable O 2 study was a mononuclear metal complex -O 2 can be adjusted in accordance with the speed of a variety of biological responses, including the bio-transformation, saengcheyi water oxidative metabolism and oxidative phosphorylation of the naturally occurring molecule in the object , The nickel peroxo complex according to the present invention controls the steric effect of the substituent of the ligand, and thus the rate of the nucleophilic reaction can be easily controlled, thereby completing the present invention.
An object of the present invention is to provide a nickel peroxide complex.
It is another object of the present invention to provide an active oxygen carrier comprising the nickel peroxo complex.
It is another object of the present invention to provide an oxidizing agent comprising the nickel peroxo complex.
It is another object of the present invention to provide a method for controlling the rate of nucleophilic oxidation reaction comprising the nickel peroxo complex.
In order to achieve the above object,
The present invention provides a nickel peroxo complex comprising a compound represented by the following general formula (1).
[Chemical Formula 1]
[Ni (L) (O 2 )] +
(In the
L is
R 1 and R 2 are independently an unsubstituted or substituted linear or branched C 1 - 10 alkyl or C 1 - 10 alkoxy, C 3 - 10 cycloalkyl, C 6 - 10 aryl or C 6 - 10 aryl C 1 - 3 is alkyl,
The substituted C 1 - 10 alkyl, C 1 - 10 alkoxy, C 3 - 10 cycloalkyl, C 6 - 10 aryl or C 6 - 10 aryl C 1- 3 alkyl, halogen, hydroxy, C 1 - 3 alkyl, and C Lt; / RTI > alkoxy, and 1 to 3 alkoxy).
The present invention also provides an active oxygen carrier comprising the nickel peroxo complex represented by the above formula (1).
Further, the present invention provides an oxidizing agent comprising the nickel peroxo complex represented by the above formula (1).
The present invention also provides a nucleophilic oxidation reaction rate control method comprising the nickel peroxo complex represented by the above formula (1).
Nickel flops oxo complexes according to the invention to include a side-on coordination bond to O 2 stably and, by controlling the steric hindrance of the supporting ligand substituents can adjust easily the reaction rate in the nucleophilic oxidation enable O 2 It can be usefully used as a mimetic substance of a metal enzyme or a biomolecule having a desired reaction rate in various biological reactions including biotransformation of a naturally occurring molecule, oxidative metabolism of a living body organism, and oxidative phosphorylation.
Figure 1 illustrates the crystal structure of (a) [Ni II (TBDAP) (NO 3 ) (H 2 O)] + and (b) [Ni II (CHDAP) (NO 3 )] + Thermal Ellipsoid Plot) Hydrogen atoms were omitted (30% probability level).
2 a is a UV-vis spectrum of [Ni II (TBDAP) (NO 3 ) (H 2 O)] + (black line) and [Ni III (TBDAP) (O 2 )] + (red line) b is [Ni (TBDAP) ( 16 O 2 )] + (phase) And [Ni (TBDAP) ( 18 O 2 )] + (lower) An ESI-MS spectrum, c is [Ni (TBDAP) (16 O 2)] + Resonance Raman spectrum, and the d is [Ni (TBDAP) (16 O 2)] + in the EPR measurement graph (red line) and simulation ( (Microwave power = 1 mW, frequency = 9.9646 GHz, sweep width = 0.15 T, control frequency = 100 kHz, and control amplitude = 1 mT).
FIG. 3 illustrates the crystal structure of [Ni III (TBDAP) (O 2 )] 2 + (ORTEP, 30% probability level).
4 is a graph of OO stretching frequency (cm -1 ) versus OO binding distance (Å) of a sidestone metal-O 2 composite (the solid curve is a straight line of the least squares method, The dots represent data collected through previously reported theories and experiments, and red represents Example 1).
5a is the UV-vis spectrum of [Ni II (CHDAP) (NO 3 )] + (black line) and [Ni III (CHDAP) (O 2 )] + (red line) CHDAP) ( 16 O 2 )] + (phase) and [Ni (CHDAP) ( 18 O 2 )] + An ESI-MS spectrum, c is [Ni (CHDAP) (16 O 2)] + and [Ni (CHDAP) (18 O 2)] and the resonance Raman spectra of +, d is [Ni (CHDAP) (16 O 2 )] + EPR measurement graph (red line) and simulation (a plot of the black line) (the parameters of the machine: the microwave power = 1 mW, frequency = 9.9646 GHz, sweep width = 0.15 T, control frequency = 100 kHz, and the control Amplitude = 1 mT).
6 shows the structure calculated by DFT of (a) [Ni (TBDAP) (O 2 )] + and (b) [Ni (CHDAP) (O 2 )] + (C, gray; N, blue; O, red; Ni, green).
FIG. 7a shows the reaction of 100 equivalents of 2-PPA with [Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) (O 2 )] + , respectively, under CH 3 CN / CH 3 OH added with shows an indicated UV-vis spectrum change, b is [Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) (O 2 )] + in the first reaction rate constant to determine the activation parameters and the 1 / shows a correlation graph of the T and, c is [Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) (O 2 )] ln K rel about + aldehyde depot wheat primary reaction rate of migration reaction of σ p + is a graph showing the Hammet plot (k rel = (p- a substituted benzaldehyde) k obs / (benzaldehyde) k obs).
8 is 25 ℃ CH 3 CN / CH 3 OH: the 2-PPA under (11), respectively [Ni (TBDAP) (O 2 )] + ( blue ■), [Ni (CHDAP) (O 2)] + (Red ◆), the secondary rate constant can be found by plotting the k obs and 2-PPA concentrations.
9 is a cyclic voltammogram of [Ni (TBDAP) Cl 2 ] (blue) and [Ni (CHDAP) Cl 2 ] (red).
10 is an ESI-MS spectrum of [Ni II (TBDAP) (NO 3 ) (H 2 O)] + .
11 is an ESI-MS spectrum of [Ni II (CHDAP) (NO 3 )] + .
Figure 12 shows a [Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) (O 2 )] + The structure of the DFT calculation rolled up.
13 is ESI-MS measured after termination of the reaction of [Ni (TBDAP) (O 2 )] + with 2-PPA.
14 is ESI-MS measured after termination of the reaction of [Ni (CHDAP) (O 2 )] + with 2-PPA.
Hereinafter, the present invention will be described in detail.
The present invention provides a nickel peroxo complex comprising a compound represented by the following general formula (1).
[Chemical Formula 1]
[Ni (L) (O 2 )] +
In Formula 1,
L is
R 1 and R 2 are independently an unsubstituted or substituted linear or branched C 1 - 10 alkyl or C 1 - 10 alkoxy, C 3 - 10 cycloalkyl, C 6 - 10 aryl or C 6 - 10 aryl C 1 - 3 is alkyl,
The substituted C 1 - 10 alkyl, C 1 - 10 alkoxy, C 3 - 10 cycloalkyl, C 6 - 10 aryl or C 6 - 10 aryl C 1- 3 alkyl, halogen, hydroxy, C 1 - 3 alkyl, and C 1 to 3 alkoxy, and the like.
And 10-cycloalkyl, - preferably wherein R 1 and R 2 are independently an unsubstituted or substituted linear or branched C 1 - 10 alkyl or C 3
The substituted C 1 - 10 alkyl or C 3 - 10 cycloalkyl, halogen, hydroxy, C 1 - may be substituted one or more by one substituent at least one selected from the group consisting of 3-alkoxy-3 alkyl and C 1.
More preferably, R 1 and R 2 are independently selected from the group consisting of unsubstituted or substituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Pentyl, n-hexyl, isohexyl, tert-hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl and n-decyl. More preferably, R 1 and R 2 are independently unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, and the like.
More preferably, R 1 and R 2 are independently unsubstituted tert-butyl or cyclohexyl.
The most preferred examples of the L ligands of the nickel peroxo complex represented by the above formula (1) according to the present invention are as follows:
(1) N, N'-di-tert-butyl-2,11-diaza [3.3] (2,6) -pyridinopane (hereinafter referred to as TBDAP).
(2) N, N'-dicyclohexyl-2,11-diaza [3.3] (2,6) -pyridinopane (hereinafter referred to as CHDAP).
Nickel flops oxo complexes of the present invention receives the donor to a non-shared electron pairs from the four N of the L supporting ligands (support ligand) around the Ni (Ⅲ) is coordinated to the N-tetradenate, O-bidentate from the buffer oxo ligand O 2 . In particular, the O 2 is characterized by a structure of coordination bond as a side-on.
In the nickel peroxo complex of the present invention, R 1 and R 2 of L, which are the supporting ligands, and O 2 which is a peroxo ligand are located in the same direction, and nickel in which the small ring structure of the supporting ligand is the central metal, O 2 side-on coordination with stable side-on superposition (nickel 3d x 2 y 2 orbitals and oxygen-oxygen half-bonds π * orbital superimposition) of nickel and O 2 by moving away from the plane.
The complexes in which oxygen is coordinated to the side-on state of metals in the past, especially those in which oxygen is coordinated to side-by-side in nickel, are structurally unstable and difficult to maintain, but the nickel peroxo complexes according to the present invention are supported on Ni Since the ligand L and the peroxide ligand O 2 are coordinated (see Experimental Example 1), various nickel peroxo complexes are formed by the introduction of the substituents R 1 and R 2 of L can do.
The present invention also provides an active oxygen carrier or oxidant comprising the nickel peroxo complex represented by the above formula (1).
The active oxygen carrier (oxidizing agent) according to the present invention can be confirmed that the aldehyde depolylation reaction with each benzaldehyde in which the para position of benzaldehyde and benzene ring are substituted with Me, F, Cl, and Br 2-2 PPA (2-phenylpropionaldehyde) and 2-PPA (2-phenylpropionaldehyde) were reacted with aldehyde to produce acetophenone in a high yield and reduced from nickel peroxo complex to nickel precursor (See Experimental Example 2-3).
Thus, the active oxygen transfer agent (oxidant) according to the present invention acts as a key intermediate in the oxygen activation cycle by heam or non-heam and metal enzymes in vivo, Can be usefully used as an active oxygen carrier for a variety of biological reactions involving the biotransformation of a molecule, oxidative metabolism of a living body, and oxidative phosphorylation.
Further, the present invention provides a method for controlling the rate of the nucleophilic oxidation reaction comprising the nickel peroxo complex represented by the above formula (1).
Specifically, in the method of controlling the nucleophilic oxidation reaction rate according to the present invention, when the reaction rate is relatively slow, it is difficult to contact with the reactant when the Ni-O 2 moiety is blocked much. Therefore, A substituent having a large steric hindrance is introduced into R 1 and R 2 of L of the nickel peroxo complex. On the other hand, when it is aimed at a relatively fast reaction rate, a space is formed in the Ni-O 2 portion to make contact with the reactant it is a step of introducing a small steric hindrance substituent on R 1, R 2 so as to be easy.
If the supporting ligand of nickel flops oxo complex according to the invention is CHDAP, steric hindrance is smaller than TBDAP [Ni (CHDAP) (O 2)] + a [Ni (TBDAP) (O 2 )] + approximately eight times the (See Experimental Example 2-3). ≪ tb >< TABLE >
In order to control the rate of the conventional nucleophilic oxidation reaction, it has been relatively difficult to control the ring of the supporting ligand of the nickel peroxo complex or to control the central metal with superoxo, oxo, peroxo, The method of controlling the reaction rate is easy because the reaction rate can be controlled according to the degree of covering the Ni-O 2 moiety by controlling the substituent having the steric hindrance of the supporting ligand.
Accordingly, the living body of a naturally occurring molecule that activates O 2 wherein the nucleophilic oxidation rate control method according to the invention by using a sterically hindered difference between the substituents of the supporting ligand has so adjustable easily the reaction rate in the nucleophilic oxidation It can be usefully used as a mimetic substance of a metal enzyme or a biomolecule having a desired reaction rate in various biological reactions including oxidation, metastasis, oxidative metabolism of a living body, and oxidative phosphorylation.
Hereinafter, the production examples, examples and experimental examples of the present invention will be specifically described as examples. However, the present invention is not limited by the following examples and experimental examples.
< Manufacturing example 1> [ Ni (TBDAP) (NO 3 ) (H 2 O)] (NO 3 )of Produce
[Chemical Formula 1]
Step 1: Preparation of TBDAP
N, N'-di-tert-butylamino) methyl] - (chloromethyl)] - pyridine was reacted with 2,6-bis- (chloromethyl) Butyl-2,11-diaza [3.3] (2,6) -pyridinophan (TBDAP).
Step 2: Preparation of [Ni (TBDAP) (NO 3 ) (H 2 O)] (NO 3 )
To a solution of acetonitrile (2 mL) in which N, N'-di-tert-butyl-2,11-diaza [3.3] (2,6) -pyridinopyran (TBDAP, 0.35 g, Ni (NO 3) 2 · 6H 2 O (0.29 g, 1 mmol) is dissolved in chloroform solution (2 mL) an added slowly, the mixture was stirred overnight and the solvent removed [Ni (TBDAP) (NO 3 ) in (H 2 O)] (NO 3 ) was prepared in the form of a blue powder (yield: 0.4 g (75%)).
< Manufacturing example 2> [ Ni ( CHDAP ) ( NO 3 )] ( NO 3 ) ( CH 3 OH )
(2)
Step 1: Preparation of CHDAP
N, N'-dicyclohexyl-2,11-di (tert-butoxycarbonyl) aminopyridine was prepared by reacting N, N '- (pyridine- (3.3) (2,6) -pyridinophan (CHDAP).
Step 2: N, N'-Dicyclohexyl-2,11-diaza [3.3] (2,6) -pyridinophan (CHDAP, 0.18 g, 0.5 mmol) obtained in the
Example 1 [Preparation of Ni Ⅲ ( TBDAP ) (O 2 )] + Manufacturing
A: Preparation of [Ni Ⅲ (TBDAP) (O 2 )] +
(3)
To a CH 3 CN (2 mL) solution of [Ni (TBDAP) (NO 3 ) (H 2 O)] (NO 3 ) (4 mM) obtained in Preparation Example 1 was added 2 equivalents of triethylamine (TEA) Equivalent amount of H 2 O 2 was reacted at 25 ° C to obtain a brown solution.
B: [Ni (TBDAP) ( 18 O 2 )] + Produce
To a CH 3 CN (2 mL) solution of [Ni (TBDAP) (NO 3 ) (H 2 O)] (NO 3 ) (4 mM) obtained in Preparation Example 1 was added 2 equivalents of TEA and 5 equivalents of H 2 18 O 2 (72 μL, 90% 18 O-enriched, 0.89% H 2 18 O 2 in water).
< Example 2> [ Ni Ⅲ ( CHDAP ) ( O 2 )] + Manufacturing
A: Preparation of [Ni Ⅲ (CHDAP) (O 2 )] +
[Chemical Formula 4]
To a CH 3 CN (2 mL) solution of [Ni (CHDAP) (NO 3 )] (NO 3 ) (CH 3 OH) (4 mM) obtained in Preparation Example 2 was added 2 equivalents of triethylamine Equivalent amount of H 2 O 2 was reacted at 25 ° C to obtain a green solution.
B: [Ni (CHDAP) ( 18 O 2 )] 2 + Produce
To a CH 3 CN (2 mL) solution of [Ni (CHDAP) (NO 3 )] (NO 3 ) (CH 3 OH) (4 mM) obtained in Preparation Example 2 was added 2 equivalents of TEA and 5 equivalents of H 2 18 O 2 (72 μL, 90% 18 O-enriched, 0.89
< Experimental Example 1 > The nickel Peroxo Structural Analysis of Composites
In order to clarify the structure of the nickel complex according to the present invention, the following physicochemical analysis was performed.
1. UV- vis spectrum
[Ni II (TBDAP) (NO 3) (H 2 O)] +, [Ni II (CHDAP) (NO 3)] +, [Ni Ⅲ (TBDAP) (O 2)] + and [Ni Ⅲ (CHDAP) (O 2 )] + was measured using a Hewlett Packard 8453 diode array spectrophotometer equipped with a UNISOKU Scientific Instruments for low-temperature experiments or a circulating water bath to examine the UV-vis spectrum. The results are shown in FIGS. 2A, Respectively.
2a shows the UV-vis spectra of [Ni II (TBDAP) (NO 3 ) (H 2 O)] + (black line) and [Ni III (TBDAP) (O 2 )] + (red line) Is the UV-vis spectrum of [Ni II (CHDAP) (NO 3 )] + (black line) and [Ni III (CHDAP) (O 2 )] + (red line).
As shown in FIG. 2A, the UV-visible spectrum absorption band (black line) of [Ni II (TBDAP) (NO 3 ) (H 2 O)] + is 645 nm (ε = 10 M -1 cm -1 ) , Ε = 10 M -1 cm -1 ) and 1066 nm (ε = 25 M -1 cm -1 ), and the UV-visibility of [Ni Ⅲ (TBDAP) (O 2 )] + The absorption spectra of the light spectrum band (red line) were ~560 nm (ε = 15 M -1 cm -1 ) and 1040 nm (ε = 45 M -1 cm -1 ).
5A, the UV-visible spectrum absorption band (black line) of [Ni II (CHDAP) (NO 3 )] + was 588 nm (? = 15 M -1 cm -1 ), 835 nm (ε = 25 M -1 cm -1 ) and 1010 nm (ε = 45 M -1 cm -1 ), and the UV-visible spectral absorption of [Ni Ⅲ (CHDAP) (O 2 )] + The band (red line) showed two absorption bands at 584 nm (ε = 35 M -1 cm -1 ) and 950 nm (ε = 70 M -1 cm -1 ).
Thus, [Ni II (TBDAP) ( NO 3) (H 2 O)] + and [Ni II (CHDAP) (NO 3)] + in the UV- visible spectrum absorption bands are similar and, [Ni Ⅲ (TBDAP) (O 2 )] + and [Ni III (CHDAP) (O 2 )] + are similar, and the nickel peroxo complex according to the present invention is a ligand of TBDAP or CHDAP, It was confirmed that the ligand of two oxygen atoms was coordinated to nickel.
2. ESI -MS ( Electrospray ionization mass spectrometry)
[Ni II (TBDAP) (NO 3 ) (H 2 O)] + , [Ni III (TBDAP) ( 16 O 2 )] + and [Ni (TBDAP) ( 18 O 2 )] + ; And [Ni II (CHDAP) (NO 3)] +, [Ni Ⅲ (CHDAP) (16 O 2)] + and [Ni (CHDAP) (18 O 2)], the injection voltage to evaluate the mass of + is (JEOL JMS-T100CS spectrometer) according to the manual, to a Waters (Milford, Mass.) Acquisite SQD quadrupole ion collector set at 2.5 kV and a capillary temperature of 80 ° C, 2b, 5b, 10, and 11, respectively.
FIG. 2B is a graph showing the relationship between [Ni (TBDAP) ( 16 O 2 )] + And [Ni (TBDAP) ( 18 O 2 )] + (phase) ESI-MS spectrum;
Figure 5b of the [Ni (CHDAP) (16 O 2)] + ( bottom) and [Ni (CHDAP) (18 O 2)] + ( a) ESI-MS spectrum;
10 is an ESI-MS spectrum of [Ni II (TBDAP) (NO 3 ) (H 2 O)] + ;
11 is an ESI-MS spectrum of [Ni II (CHDAP) (NO 3 )] + .
As shown in Figure 2b, [Ni (TBDAP) ( 16 O 2)] + in ESI-MS spectra showed significantly from m / z 442.2, which [Ni (TBDAP) (16 O 2)] + (calcd corresponds with m / z 442.2), [Ni (TBDAP) (18 O 2)] + in ESI-MS spectra were observed in m / z 446.2, which [Ni (TBDAP) (18 O 2)] + (calcd m / z 446.2).
As shown in Figure 5b, [Ni (CHDAP) ( 16 O 2)] + in ESI-MS spectra showed significantly from m / z 494.2, which [Ni (CHDAP) (16 O 2)] + (calcd m / z 494.2) and a corresponding and, [Ni (CHDAP) (18 O 2)] ESI-MS spectrum of + appeared significantly at m / z 498.2, which [Ni (CHDAP) (18 O 2)] + (calcd m / z 498.2).
The m / z values of 16 O 2 (m / z 442.2) and 18 O 2 (m / z 446.2) or 16 O 2 (m / z 494.2) and 18 O 2 The nickel peroxo complexes according to the invention showed that the ligands of the two oxygen atoms were coordinated to nickel.
As shown in FIG. 10, the ESI-MS spectra of [Ni II (TBDAP) (NO 3 ) (H 2 O)] + are present at three ion peaks at 225.6, 246.1 and 472.2 m / z, Ni (TBDAP) (CH 3 CN)] 2+ (calcd m / z 225.6), [Ni (TBDAP) (CH 3 CN) 2 ] 2+ (calcd m / z 246.1) 3 )] + (calcd m / z 472.2).
As shown in Figure 11, [Ni II (CHDAP) (NO 3)] ESI-MS spectrum of + is present in the two ion peaks at 251.7, 524.3 m / z, respectively, which [Ni (CHDAP) (CH 3 CN)] 2 + (calcd m / z 251.6) and [Ni (CHDAP) (NO 3 )] + (calcd m / z 524.2).
Therefore, the nickel peroxo complex according to the present invention confirmed that the ligand of TBDAP or CHDAP was coordinated to nickel.
3. Resonance Raman Spectrum
To measure the Raman spectrum of [Ni (TBDAP) ( 16 O 2 )] + , [Ni (CHDAP) ( 16 O 2 )] + and [Ni (CHDAP) ( 18 O 2 )] + , 1200 groovs / mm The resonance Raman spectrum was measured using a liquid nitrogen cooled CCD detector (CCD-1024x256-OPEN-1LS, HORIBA Jobin Yvon) attached to a 1 m single polychromator (MC-100DG, Ritsu Oyo Kogaku) having a holographic grating .
Specifically, an excitation wavelength of 441.6 nm was provided by supplying a power of 20 mW to the sample point using a He-Cd laser (Kimmon Koha, IK5651R-G and KR1801C). All measurements were carried out at -20 캜, CD 3 CN using a rotary vessel (1000 rpm). The Raman shift was calibrated using indine and the peak position accuracy in the Raman band was ± 1 cm -1 . v (OO) is determined based on the correlation between the OO bond length and the OO stretching frequency and its frequency, and the results are shown in Figs. 2C and 5C.
Figure 2C is the resonance Raman spectrum of [Ni (TBDAP) ( 16 O 2 )] +
5C is a resonance Raman spectrum of [Ni (CHDAP) ( 16 O 2 )] + and [Ni (CHDAP) ( 18 O 2 )] +
As shown in FIG. 2C, the resonance Raman spectrum of [Ni (TBDAP) ( 16 O 2 )] + collected at -20 ° C. using excitation of 422 nm in CD 3 CN shows 989 cm -1 , And the resonance Raman spectrum of [Ni (CHDAP) ( 16 O 2 )] + was 988 cm -1 . The value of a side-on nickel-oxo-flops shown in the complex [Ni (12-TMC) ( O 2)] + (1002 cm -1) and [Ni (13-TMC) ( O 2)] + (1008 cm -1 ), Where 12-TMC is 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane, 13-TMC is 1,4 , 7,10-tetramethyl-1,4,7,10-tetraazacyclotridecane).
In addition, the resonance Raman spectra of the [Ni (CHDAP) (18 O 2)] + are replaced with 18 O exhibits a 919 cm -1, it can be seen that the isotopically a sensational band.
Thus, [Ni (CHDAP) (O 2)] + of OO stretching vibration is [Ni (TBDAP) (O 2 )] and found to be very similar to the OO stretching vibration of +, nickel according to the present invention from which the buffer The oxo complex is O 2 It can be confirmed that the ligand of the part is coordinated with the side-on.
4. Effective magnetic moment measurement
To determine the nickel spin states of [Ni (TBDAP) ( 16 O 2 )] + and [Ni (CHDAP) ( 16 O 2 )] + , the effective magnetic moment was measured.
The effective magnetic moment was determined using Evans' modified 1 H NMR method at room temperature. A WILMAD coaxial insertion tube (sealed capillary) containing an acetonitrile-d 3 solution (with 1.0% tetramethylsilane) (blank) Was injected into a general NMR tube containing [Ni (TBDAP) ( 16 O 2 )] + and [Ni (CHDAP) ( 16 O 2 )] + dissolved in acetonitrile-d 3 solution (with 0.3% TMS). The chemical shift of the TMS peak (or solution peak) in the presence of the paramagnetic metal complex was calculated using the
[Formula 1]
mu = 0.0618 (? vT / 2fM) 1/2
(In the
f is the vibrator frequency (MHz) of the superconducting spectrometer,
T is the absolute temperature,
M is the molar concentration of the metal ion,
Δv is the frequency difference (Hz) between the two reference signals.)
The spin states of [Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) ( 16 O 2 )] + analyzed by the above method are as follows.
[Ni (TBDAP) (O 2 )] + : 2.3 μ B S = 1/2 Low spin state.
[Ni (CHDAP) ( 16 O 2 )] + : 2.2 μ B S = 1/2 Low spin state.
Therefore, it can be confirmed that the nickel peroxo complex according to the present invention has the same spin state of nickel.
5. Electron resonance paramagentic resonance)
The EPR was performed to determine the nickel electron arrangement and spin quantification of [Ni (TBDAP) ( 16 O 2 )] + and [Ni (CHDAP) ( 16 O 2 )] +
Specifically, the continuous-wave EPR spectra were performed using an X-Band Bruker EMX-plus spectrometer equipped with a dual mode cavity at 20 K (absolute temperature) and CH 3 CN (ER 4116 DM). Oxford Intruments ISR900 liquid-helium quartz cryostat, Oxford Instruments ITC503, and a gas inlet controller. Various quantities of CuCl 2 were used as the EPR standard (equipment parameters: microwave power = 1 mW, frequency = 9.9646 GHz, sweep width = 0.15 T, control frequency = 100 kHz, = 1 mT), and the results are shown graphically in Figs. 2d and 5d.
2d is an EPR measurement graph of [Ni (TBDAP) ( 16 O 2 )] + (equipment parameters: microwave power = 1 mW, frequency = 9.9646 GHz, sweep width = 0.15 T, control frequency = 100 kHz, Amplitude = 1 mT);
5D is a graph of EPR measurement of [Ni (CHDAP) ( 16 O 2 )] + (equipment parameters: microwave power = 1 mW, frequency = 9.9646 GHz, sweep width = 0.15 T, Adjustment amplitude = 1 mT).
As shown in Figure 2D, the X-band electron photomagnetic resonance (EPR) of Ni (TBDAP) ( 16 O 2 )] + showed an axial signal with values of 2.19 g and 2.02 g. This is the typical (d z 2 ) 1 electron configuration observed in nickel (III) complexes. 89% of the total nickel content in the EPR reference corresponds to a determination of spin in the EPR signal.
Further, as shown in FIG. 5D, the EPR spectrum of [Ni (CHDAP) ( 16 O 2 )] + showed an axial signal having g values of 2.17 g and 2.03. This is the typical (d z 2 ) 1 electron configuration observed in nickel (III) complexes. 95% of the total nickel content in the EPR reference corresponds to a quantitation of the spin in the EPR signal.
Therefore, it was confirmed that the nickel peroxo complex according to the present invention is a nickel (III) peroxo complex coordinated with a side-on.
6. X-ray crystal analysis
[Ni II (TBDAP) (NO 3) (H 2 O)] +, to the [Ni II (CHDAP) (NO 3)] +, [Ni Ⅲ (TBDAP) (O 2)] 2 + crystal structure analysis of The following measurements were made.
Specifically, [Ni (TBDAP) (NO 3 ) (H 2 O)] (NO 3 ), [Ni (CHDAP) (NO 3 )] (NO 3 ) (CH 3 OH) 2 )] (ClO 4 ) (0.5CH 2 Cl 2 ) (obtained by slowly diffusing Et 2 O in the presence of NaClO 4 in the CH 2 Cl 2 solution of Example 1) was measured using a nylon loop (Hampton Research Co.) Was taken from the solution at ca.-40 ° C on a hand-made copper dish placed inside a liquid nitrogen Dewar vessel and placed on a GH (goniometer head) in N 2 Cryostream. Data collection was performed under a Mo Kα (λ = 0.71073 Å) incident beam using a Bruker SMART AXS diffractometer equipped with a monochromator. The Bruker-SAINT software package was used to integrate and extend the CCD data, and the structure was analyzed and refined using SHELXTL Version 6.12. The hydrogen atoms other than the hydrogen in the water are located at the calculated points, and the hydrogen atoms located in the water are shown on the Fourier difference map. All non-hydrogen atoms were refined by anisotropic thermal parameters and analyzed by X-ray crystallography. The results are shown in Table 1 (X-ray crystallographic figure), Table 2 (joining distance and angle), and Figs. 1, 3 and 4.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates the crystal structure of (a) [Ni II (TBDAP) (NO 3 ) (H 2 O)] + and (b) [Ni II (CHDAP) (NO 3 )] + Thermal Ellipsoid Plot) Hydrogen atoms were omitted (30% probability level)
3 is an illustration of the crystal structure of [Ni Ⅲ (TBDAP) (O 2 )] 2 + (ORTEP, 30% probability level);
4 is a graph of OO stretching frequency (cm -1 ) versus OO binding distance (Å) of a sidestone metal-O 2 composite (the solid curve is a straight line of the least squares method, The dots represent data collected through previously reported theories and experiments, and red represents Example 1).
wR2 = 0.1037
wR2 = 0.0702
wR2 = 0.0820
wR2 = 0.1239
wR2 = 0.0713
wR2 = 0.0874
(In Table 1 and 2, Preparation 1 [Ni (TBDAP) (NO 3 ) (H 2 O)] (NO 3), Production Example 2 [Ni (CHDAP) (NO 3 )] (NO 3) ( CH 3 OH), Example 1 is [Ni (TBDAP) (O 2 )] (ClO 4 ) (0.5CH 2 Cl 2 )
As shown in 1, 3 and Table 1, [Ni (TBDAP) ( NO 3) (H 2 O)] (NO 3), [Ni (CHDAP) (NO 3)] (NO 3) (
As shown in Table 2, the OO bond length (1.401 (2) Å) of [Ni (TBDAP) (O 2 )] (ClO 4 ) (0.5CH 2 Cl 2 ) -TMC) (O 2)] + (1.386 Å) and [Ni (13-TMC) ( O 2)] + (1.383 Å) and the like, spread-oxo category (~ 1.4 it can be seen corresponding to 1.5 Å) .
4, the OO bond length and the OO stretching frequency of [Ni (TBDAP) (O 2 )] (ClO 4 ) (0.5CH 2 Cl 2 ) are determined by the stretching frequency of the side- It can be seen that O 2 is coordinated to the side-on.
Therefore, it can be confirmed that the nickel peroxo complex according to the present invention is a hexel coordination nickel (III) ion structure, and the O 2 is a nickel peroxo complex having a side-on coordination.
7. Density Functional Theory
Density Functional Theory (DFT) was performed to evaluate the structural similarities and differences between [Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) (O 2 )] + according to the present invention.
Specifically, spin-polarized DFT calculations were performed using a planar-
Calculated by performing a DFT [Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) (O 2 )] showed the structure of the + 6, the calculated [Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) (O 2 )] showed 12 rolled up the structure of the +, DFT calculated [Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) for quantitative comparison (O 2 )] + And the bond length of [Ni (TBDAP) (O 2 )] + calculated by X-ray in Experimental Example 1-6 are shown in Table 3.
6 shows the structure calculated by DFT of (a) [Ni (TBDAP) (O 2 )] + and (b) [Ni (CHDAP) (O 2 )] + (C, gray; N, blue; O, red; Ni, green);
Figure 12 is the calculated DFT [Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) (O 2 )] will overlap the structure shown in +;
Table 3 summarizes the results of the measurements of [Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) (O 2 )] + (DFT) 2 )] + Ni-O (average length), Ni-N equatorial (average length), Ni-N axial (average length) and OO (average length).
As shown in FIG. 6, (a) [Ni (TBDAP) (O 2 )] + and (b) [Ni (CHDAP) (O 2 )] + are side-on type having octahedral metal ligand atoms It can be confirmed that it is a nickel peroxo complex.
As shown in FIG. 12, the structural difference between [Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) (O 2 )] + can be seen at a glance. In particular, the tert-butyl moiety and the cyclohexyl moiety are different, and the degree of covering the NiO 2 moiety is different.
As shown in Table 3, since they all have similar coupling lengths, reliability is given in the structural analysis of FIGS. 6 and 12, and only the average Ni-N axial coupling length is relatively larger than the average Ni-N equatorial coupling length, It is a phenomenon due to the Jahn-Teller effect, which occurs in the spin d 7 e disposed.
Therefore, the nickel peroxo complex according to the present invention is similar to the structure of the side-on type but has a structural difference in the supporting ligand, so that the steric hindrance that obscures the center of NiO 2 may be different.
< Experimental Example 2> The nickel Peroxo Evaluation of reactivity of complex
1. Redox ( Redox ) Reactivity
In order to evaluate the redox reactivity of the nickel peroxo complex according to the present invention, it was measured by cyclic voltammetry.
Specifically, [Ni (TBDAP) Cl 2 ] and [Ni (CHDAP) Cl 2 ] were treated with CH 3 CN (1 mM) containing 0.1 M Bu 4 NClO 4 as a working electrode to Pt, The reference electrode was measured with Ag / Ag + scan rate = 100 mV, and the results are shown in FIG. 9 and Table 4.
9 is a cyclic voltammogram of [Ni (TBDAP) Cl 2 ] (blue) and [Ni (CHDAP) Cl 2 ] (red).
Ni (II) containing the 9 and Table 4. Referring, to TBDAP and CHDAP each chloride complex is relatively, E 1/2 are 0.56 and 0.57 V gave a reversible redox couple (vs Fc + / Fc (V )) quot; refers to a quasi-reversible redox couple, which corresponds to one electron oxidation from nickel (II) to nickel (III).
Therefore, it can be seen that the redox couples are almost similar, so that the nickel peroxo complexes according to the present invention have a similar redox reaction tendency.
2. Nucleophilic or Electrophilic evaluation
The nickel peroxo complex according to the present invention was reacted with the nickel peroxo compound of the present invention and para-substituted benzaldehyde in order to examine whether the nickel peroxo complex according to the present invention functions as nucleophilic or electrophilic in the aldehyde demethylation reaction.
Specifically, the benzaldehyde and benzene respective benzaldehyde was the para-position of the ring-substituted with Me, F, Cl, and Br [Ni (TBDAP) (O 2)] + or [Ni (CHDAP) (O 2 )] + And aldehyde diafiltration reaction, and the primary reaction rate constants of the reaction were measured. The results are shown in Table 5. The value of k rel (k) calculated by (k-substituted benzaldehyde) k obs / (benzaldehyde) k obs Figure 7c is a Hammet plot of ln K rel and σ p + .
FIG. 7C is a graph showing the Hammet plot of ln K rel and σ p + with respect to the primary reaction rate of the aldehyde demation reaction.
As shown in FIG. 7C, the value of Hammett ρ is 4.4 ([Ni (TBDAP) (O 2 )] + ) and 4.3 ([Ni (CHDAP) (O 2 )] + ). This amount of Hammett ρ indicates the nucleophilic nature.
Therefore, it can be confirmed that the nickel peroxo complex according to the present invention has a nucleophilic property in an aldehyde demethylation reaction.
3. Aldehyde Depollution ( Aldehyde deformylation ) Reactivity
In order to evaluate the aldehyde demethylation reactivity of the nickel peroxo complex according to the present invention, the following experiment was conducted.
Specifically, 2-PPA ( 2 ) is added to [Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) (O 2 )] + formed at 25 ° C under CH 3 CN / CH 3 OH (1: 2-propionaldehyde) were added and reacted. All reactions were carried out by observing the UV-vis changes of the reaction solutions in a 1 cm UV cuvette and shown in FIG. 7a. The reaction rate constants were determined by UV-vis spectroscopy at 560 nm of [Ni (TBDAP) (O 2 )] + Vis change and UV-vis change at 934 nm of [Ni (CHDAP) (O 2 )] + are shown in Fig. 7b. The change in the reaction rate of the
The reactions were performed at least three times and the mean values of the reactions were used as data. The product was analyzed by direct injection of the reaction mixture into high performance liquid chromatography (HPLC), the product was identified by comparison with certified samples, and the product yield was compared to the reference range of certified samples prepared as internal standards. After the oxidation reaction of [Ni (TBDAP) (O 2 )] + and 2-PPA as a reaction product, acetophenone (71 ± 5%) was produced, and [Ni (CHDAP) (O 2 )] + - Acetophenone (90 ± 5%) was generated after the oxidation reaction of PPA.
Figure 7 is showing a [Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) (O 2 )] + a (a) UV-vis, ( b) correlation between the first order reaction rate constant and 1 / T Graph,
8 is 25 ℃ CH 3 CN / CH 3 OH: the 2-PPA under (11), respectively [Ni (TBDAP) (O 2 )] + ( blue ■), [Ni (CHDAP) (O 2)] + (red ◆) and the reaction was graph showing the k obs and 2-PPA concentration obtained.
13 is ESI-MS measured after termination of the reaction of [Ni (TBDAP) (O 2 )] + with 2-PPA.
14 is ESI-MS measured after termination of the reaction of [Ni (CHDAP) (O 2 )] + with 2-PPA.
As shown in FIG. 7A, it is confirmed that the characteristic UV-vis absorption band of the reactants ([Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) (O 2 )] + .
As shown in Figure 7b, the activity measurement of [Ni (TBDAP) (O 2 )] + in the aldehyde demation reaction between 278K and 308K from the correlation of the primary reaction rate constant with 1 / T is ΔH ‡ = 67 kJ mol -1 and ΔS ‡ = -62 J mol - 1 K -1 , and, [Ni (CHDAP) (O 2)] + is the active measurement of △ H ‡ = 66 kJ mol - 1 and ΔS ‡ = -48 J mol - 1 K -1 , indicating that there is a difference in each activity measurement.
Ni (TBDAP) (O 2 )] + (k 2 = 7.4 × 10 -3 m -1 s -1 ) and Ni (CHDAP) (O 2 ) + from the slope of the graph, (k 2 = 6.2 × 10 -2 m -1 s - 1) 2 primary and shows a rate constant value, from which the [Ni (CHDAP) (O 2 )] + a [Ni (TBDAP) (O 2 ) of ] + , The reaction rate of the aldehyde depolylation is about 8 times faster.
As shown in FIG. 13, it can be confirmed that the [Ni (TBDAP) (O 2 )] + was reduced to the nickel (II) precursor through the data shown in the ESI-MS to complete the aldehyde depoilation reaction.
As shown in FIG. 14, it can be confirmed that the [Ni (CHDAP) (O 2 )] + was reduced to the nickel (II) precursor through the data shown in the ESI-MS to complete the aldehyde demation reaction.
Thus, the nickel peroxo complex of [Ni (TBDAP) (O 2 )] + and [Ni (CHDAP) (O 2 )] + reacts completely with 2-PPA as an active oxygen carrier and oxidizes 2-PPA to acetophenone The same reaction process is performed, which is reduced to a precursor, respectively, but in a kinetic analysis. [Ni (CHDAP) (O 2 )] + a [Ni (TBDAP) (O 2 )] + than showed a fast response time difference of about 8 times, reaction activity measurements also [Ni (CHDAP) (O 2 ) ] + Reacts faster than [Ni (TBDAP) (O 2 )] + . This suggests that TBDAP, a supporting ligand, is more steric hindered than CHDAP.
Accordingly, the nickel peroxo complex of the present invention can control the reactivity according to steric hindrance of various substituents of the supporting ligand, and the reaction rate can be controlled according to the required reaction rate depending on the purpose.
Specifically, when a slow reaction rate is required, the reaction rate can be slowed down by introducing a substituent having a large steric hindrance to the supporting ligand of the nickel peroxo complex. When a fast reaction rate is required, the supporting ligand of the nickel peroxide complex has a small steric hindrance The reaction rate can be increased by introducing a substituent.
Nickel flops oxo complexes according to the invention to include a side-on coordination bond to O 2 stably and, by controlling the steric hindrance of the supporting ligand substituents can adjust easily the reaction rate in the nucleophilic oxidation enable O 2 It can be usefully used as a mimetic substance of a metal enzyme or a biomolecule having a desired reaction rate in various biological reactions including biotransformation of a naturally occurring molecule, oxidative metabolism of a living body organism, and oxidative phosphorylation.
Claims (9)
The method comprises controlling the reaction rate by controlling the steric hindrance of R 1 or R 2 of L. The method of controlling the rate of the nucleophilic oxidation reaction comprises:
[Chemical Formula 1]
[Ni (L) (O 2 )] +
(In the formula 1,
L is
R 1 and R 2 are independently an unsubstituted or substituted linear or branched C 1-10 alkyl or C 1-10 alkoxy, C 3-10 cycloalkyl, C 6-10 aryl or C 6-10 aryl C 1- 3 is alkyl,
The substituted C 1-10 alkyl, C 1-10 alkoxy, C 3-10 cycloalkyl, C 6-10 aryl or C 6-10 aryl C 1-3 alkyl is halogen, hydroxy, C 1-3 alkyl and C 1 > to 3 < / RTI > alkoxy).
Wherein R 1 and R 2 are independently straight or branched C 1-10 alkyl or C 3-10 cycloalkyl.
Wherein R 1 and R 2 are independently tert-butyl or cyclohexyl.
Wherein the nucleophilic oxidation reaction is an aldehyde demethylation.
Wherein the greater the steric hindrance of R 1 or R 2 of L, the slower the reaction rate.
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