Supporting Information Structure-Reactivity Relationship of Piperidine Nitroxide: Electrochemical, ESR and Computational Studies Toshihide Yamasaki a, Fumiya Mito a, Yuko Ito a, Sokkar Pandian b, Yuichi Kinoshita a, Koji Nakano c, Ramachandran Murugesan b,d, Kiyoshi Sakai e, Hideo Utsumi e, Ken-ichi Yamada a, * a Department of Bio-functional Science, Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Higashi-ku, Maidashi, Fukuoka 812-8582, Japan b School of Chemistry, Madurai Kamaraj University, Madurai-625021, India c Department of Applied Chemistry, Graduate School of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan d Networking Resource Center in Biological Sciences, Madurai Kamaraj University, Madurai-625021, India e Innovation Center for Medical Redox Navigation, Kyushu University, 3-1-1 Higashi-ku, Maidashi, Fukuoka 812-8582, Japan toshihide@pch.phar.kyushu-u.ac.jp *Corresponding author: Ken-ichi Yamada Department of Bio-functional Science, Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Higashi-ku, Maidashi, Fukuoka 812-8582, Japan Phone: +81-92-642-6624; Fax: +81-92-642-6626 E-mail: yamada@pch.phar.kyushu-u.ac.jp S1
Table of contents Figure S1. Figure S2. Figure S3. Figure S4. Figure S5. Figure S6. Figure S7. Figure S8. Figure S9. Figure S10. Figure S11. Figure S12. Figure S13. Figure S14. Figure S15. 1 H NMR spectrum of 10 S3 13 C NMR spectrum of 10 S4 1 H NMR spectrum of 11 S5 13 C NMR spectrum of 11 S6 1 H NMR spectrum of 12 S7 13 C NMR spectrum of 12 S8 1 H NMR spectrum of 13 S9 13 C NMR spectrum of 13 S10 1 H NMR spectrum of 14 S11 13 C NMR spectrum of 14 S12 1 H NMR spectrum of 15 S13 13 C NMR spectrum of 15 S14 1 H NMR spectrum of 17 S15 13 C NMR spectrum of 17 S16 Correlation between nitroxide SM-ascorbate HM energy gap and reduction rate of nitroxide radicals S17 TABLE S1. ESR parameters of nitroxides S18 TABLE S2. Calculated descriptors of the nitroxide radicals S19 quantum chemical coordinates and total energy of nitroxide S20~S33 S2
Figure S1. 1 H NMR spectrum of 10 (400 MHz, CDCl 3 ) N H S S3
Figure S2. 13 C NMR spectrum of 10 (75 MHz, CDCl 3 ) N H S S4
Figure S3. 1 H NMR spectrum of 11 (400 MHz, CDCl 3 ) N H S S5
Figure S4. 13 C NMR spectrum of 11 (75 MHz, CDCl 3 ) N H S S6
Figure S5. 1 H NMR spectrum of 12 (400 MHz, CDCl 3 ) N H S7
Figure S6. 13 C NMR spectrum of 12 (75 MHz, CDCl 3 ) N H S8
Figure S7. 1 H NMR spectrum of 13 (400 MHz, CDCl 3 ) N H S9
Figure S8. 13 C NMR spectrum of 13 (75 MHz, CDCl 3 ) N H S10
Figure S9. 1 H NMR spectrum of 14 (400 MHz, CDCl 3 ) N H N Ac S11
Figure S10. 13 C NMR spectrum of 14 (75 MHz, CDCl 3 ) N H N Ac S12
Figure S11. 1 H NMR spectrum of 15 (300 MHz, CDCl 3 ) N H S 2 S13
Figure S12. 13 C NMR spectrum of 15 (75 MHz, CDCl 3 ) N H S 2 S14
Figure S13. 1 H NMR spectrum of 17 (300 MHz, CDCl 3 ) N H S S15
Figure S14. 13 C NMR spectrum of 17 (75 MHz, CDCl 3 ) N H S S16
Figure S15. Correlation between nitroxide SM-ascorbate HM energy gap and reduction rate of nitroxide radicals S17
TABLE S1. ESR parameters of nitroxides Nitroxide g-value 1 2.0063 ±2.08 10-5 2 2.0060 ±0.29 10-3 3 2.0060 ±4.48 10-5 4 2.0062 ±0.42 10-5 5 2.0063 ±2.93 10-5 6 2.0063 ±2.02 10-5 7a 2.0064 ±1.22 10-5 7b 2.0060 ±0.24 10-5 8a 2.0065 ±1.81 10-5 8b 2.0061 ±1.42 10-5 8c 2.0060 ±4.29 10-5 hfc (mt) 1.418 ±4.33 10-3 1.465 ±0.71 10-3 1.529 ±0.71 10-3 1.407 ±5.60 10-3 1.374 ±3.07 10-3 1.364 ±3.23 10-3 1.359 ±0.71 10-3 1.472 ±0 1.295 ±2.56 10-3 1.445 ±1.22 10-3 1.49 ±0.28 10-2 Line width (µt) 36.66 ±0.40 111.43 ±1.73 183.11 ±1.48 301.96 ±2.12 292.72 ±1.64 282.59 ±1.24 219.93 ±1.53 195.39 ±6.17 291.10 ±1.25 221.86 ±7.72 263.79 ±2.24 S18
TABLE S2. Calculated descriptors of the nitroxide radicals Nitroxide SM energy (au) SM- HM A Energy (au) Signal decay rate (min -1 ) Accessible surface area (Å 2 ) 1-0.0442 0.0439 0.427 22.5 2-0.0382 0.0495 0.031 14.6 3-0.0247 0.0601 0.004 8.6 4-0.0437 0.0458 0.126 23.1 5-0.0484 0.0408 0.543 18.5 6-0.0517 0.0336 2.469 23.1 7a -0.0499 0.0343 4.592 23.8 7b -0.0477 0.0385 1.292 23.1 8a -0.0678 0.0035 3.460 9.3 8b -0.0555 0.0230 1.057 12.6 8c -0.0420 0.0373 0.106 15.9 *HM A is corresponding energy values for ascorbate. S19
nitroxide 1 CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z ------------------------------------------------------------ H 1.0 0.5661092799 1.6259793393-1.5391637890 H 1.0-1.5023143886 1.2501524041-1.2317072138 H 1.0 2.2927093193 1.3397140134-1.6446120478 8.0-0.3226462889 2.8099848501 1.2283306079 H 1.0 2.0307906791 1.7727320991 0.8928355585 C 6.0 1.3281360691 0.8560177872-1.5306033156 C 6.0-0.1082112978 1.6107917968 1.2167414854 H 1.0 1.1726576869 0.1999152727-2.3810438222 H 1.0-2.9798847511 0.3846566420-0.8548439795 H 1.0-1.7957408211-0.3398528749-1.9359731133 C 6.0-1.9180332881 0.2673828162-1.0447921013 H 1.0 2.6569705588-1.4817131659-1.0145331413 H 1.0-2.1720579373 1.0152569845 1.5204820364 C 6.0 1.2872247845 0.9906654794 1.0209731617 C 6.0 1.3146743353 0.0368357656-0.2076434055 C 6.0-1.2021423485 0.5419673854 1.3932111615 C 6.0-1.2487485637-0.4265882098 0.1766713561 C 6.0 2.6003120182-0.8317017675-0.1476406635 H 1.0-3.0856716996-1.3821750367 0.8541604686 H 1.0 1.5365726884 0.4244162904 1.9158294436 H 1.0 3.4795383973-0.1953258281-0.1313682582 N 7.0 0.1509063159-0.9231713041-0.1070880346 H 1.0-0.9787861305-0.0280855737 2.2925150177 C 6.0-2.0848093715-1.6786477620 0.5564177203 8.0 0.1612901288-1.8328607951-1.1341950019 H 1.0 2.5961943597-1.4463169829 0.7465782291 H 1.0-2.1588489277-2.3534306522-0.2899947135 H 1.0-1.6161918068-2.2066049732 1.3804663541 TTAL ENERGY = -547.4181438425 nitroxide 2 CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z ------------------------------------------------------------ S20
H 1.0-1.0468338875-1.6592948770 1.9124222147 C 6.0-2.1921204568-2.3965629278 0.2475694855 C 6.0-1.6755018968-1.2421671961 1.1288098134 H 1.0-2.5321077270-0.7849749682 1.6203967637 H 1.0 2.9827549578-1.0504082876 1.1612418386 8.0 0.5933459395-1.6537526666-0.6466089800 H 1.0-0.5394460962 0.5738500412 2.5143141908 N 7.0 0.5474093685-0.5931460154 0.2148708064 H 1.0 3.0581472654-1.2877587342-0.5834191363 C 6.0 3.0022166055-0.5422785265 0.2027144519 C 6.0-0.8533323118-0.0819439805 0.4637661342 H 1.0 1.9404671275 0.9475593863 2.1031284779 H 1.0-0.4328657278-0.2674965314-2.4618402558 C 6.0-0.7715116871 1.0332889534 1.5562876975 H 1.0 3.8894438102 0.0812673489 0.1550430015 C 6.0 1.7300769858 0.3319698956 0.0319500204 H 1.0-1.7364339922 1.5251763959 1.6403825636 H 1.0-1.8766653889-1.1949219703-2.1035383727 C 6.0 1.7113310736 1.4149314005 1.1480216225 C 6.0-1.4636542321-0.1952199049-2.1374059286 H 1.0-2.6373691341 0.6115385138-0.5213933685 C 6.0-1.5841410919 0.5338585697-0.7831147029 C 6.0 0.3237951259 2.0677242645 1.2506701984 8.0 0.1157086685 3.2593100570 1.1050885511 H 1.0 1.7681927311 0.2643232970-2.1507906510 H 1.0 2.4701685237 2.1647574246 0.9423500622 C 6.0 1.7801698812 1.0124876840-1.3655008847 H 1.0-2.0101437382 0.3687475270-2.8877518685 H 1.0-1.2286740565 1.5524162305-0.9186314616 H 1.0 2.6999643277 1.5814101144-1.4541260744 H 1.0 0.9488371299 1.6916168781-1.5146448242 H 1.0-2.6154742264-3.1638192858 0.8893632512 H 1.0-1.3923960467-2.8406150955-0.3338506625 H 1.0-2.9733478237-2.0618770148-0.4257599742 TTAL ENERGY = -624.5648476216 nitroxide 3 CRDINATES F ALL ATMS ARE (ANGS) S21
ATM CHARGE X Y Z ------------------------------------------------------------ H 1.0 1.8241513873-1.5315633167 1.1560411849 H 1.0-1.6376786272 0.0295317905 2.2956930712 H 1.0 0.6982271506 0.2821226522 2.3897709616 H 1.0-2.2264486944 2.1178382238 0.7999725032 H 1.0-2.0255033822-2.3846747278 2.4656633218 8.0 0.0989389697-1.4921452364-0.7258060575 C 6.0 2.3253481186-0.7474643667 0.5933391781 H 1.0-3.0140670246-0.4464927331 1.3457869258 C 6.0-1.9298187379-0.5112861650 1.3995484364 H 1.0 3.0689958908-0.3113394941 1.2572873853 C 6.0 3.0663483821-1.3864569017-0.5981312455 C 6.0 0.9545935691 1.0481671636 1.6609765264 C 6.0-1.2557043708 1.7531034443 0.4743727793 N 7.0 0.0157010021-0.2122195101-0.2910584422 C 6.0-1.5234484993-1.9865529049 1.5885650199 8.0-0.2990095010 3.0227635377 2.3077429923 H 1.0-0.4542238890-2.0804384922 1.7453619944 C 6.0 1.2760246455 0.3776703204 0.2920713262 H 1.0 1.8386279082 1.5616083801 2.0300237197 H 1.0-0.9876006439 2.3018323868-0.4261643514 C 6.0-1.3528846470 0.2367386557 0.1399837376 C 6.0-0.2105340655 2.0570459783 1.5698081152 H 1.0-1.7952166506-2.5970754095 0.7357760740 H 1.0 2.1325208931 2.0361331636-2.7346273047 C 6.0 1.8739959270 1.4746874496-0.6632949554 H 1.0-1.9546730555-1.9338867840-1.7140470499 C 6.0-2.3264003562 0.1226117089-1.0844774179 H 1.0 2.9392281893 1.5549184475-0.4584066319 H 1.0-3.2059554058 0.7206434529-0.8537634965 C 6.0 1.6528798829 1.2411838491-2.1706034905 H 1.0 1.4398987299 2.4381651356-0.4082778309 H 1.0-1.8359313109 0.5936825413-1.9332231040 C 6.0-2.7963521973-1.2847245641-1.5020069707 H 1.0 0.5945653624 1.2470545876-2.4068607808 H 1.0 2.0658988475 0.2952262153-2.4996015004 H 1.0-3.4053942585-1.7435124311-0.7308190196 H 1.0-3.4021019257-1.2035926716-2.3999042963 S22
H 1.0 3.6832661579-0.6605680879-1.1162793997 H 1.0 2.3717461462-1.8268174854-1.3040525826 H 1.0 3.7179880831-2.1719158025-0.2263743250 TTAL ENERGY = -701.7122335252 nitroxide 4 CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z ------------------------------------------------------------ H 1.0-4.4937492045-0.9884537080 1.4626789348 H 1.0-2.6647731247-1.6854916170 0.1457597703 H 1.0-2.0155538172-1.6870598476 1.7701619790 H 1.0-3.5196041099 0.0013358060 2.5205527597 C 6.0-2.3986106412-1.0444999706 0.9816347517 C 6.0-3.6567328038-0.2945810293 1.4834978454 8.0-0.4618469085-1.8432018537-0.8905362154 H 1.0 1.9323965765-2.3068547702-0.9523856016 H 1.0 2.0957779300-2.2423978584 0.7880837243 H 1.0-3.7095558031 0.0035128506-1.2840046742 C 6.0-3.9916828819 0.9566454143 0.6275225597 N 7.0-0.1044848226-0.9886678278 0.1218466734 C 6.0-1.2621919227-0.0894649354 0.5118157583 H 1.0-0.6796938890 0.1673617631 2.5864523938 C 6.0 2.2361729266-1.6707575601-0.1256503059 C 6.0-3.3290794637 0.8776276879-0.7607494269 H 1.0-1.4277731478 0.3775319947-1.6153087348 H 1.0 4.2655373875-2.1722842222-0.6298000535 C 6.0-1.7839844086 0.7939055074-0.6788833669 C 6.0-0.8063448820 0.7966179538 1.7082535106 C 6.0 1.2902493962-0.4343272587-0.0980835531 H 1.0-1.5590493028 1.5455963974 1.9293688612 H 1.0 1.7760499275-0.1642510874 1.9996574189 C 6.0 3.7294598715-1.2926754909-0.2813376732 H 1.0-3.6037315050 1.7484532898-1.3520234964 H 1.0 0.6045096585 0.1033652721-2.1008472714 H 1.0 4.1467548940-1.0340853324 0.6886186440 C 6.0 1.6526438539 0.4644777010 1.1206266887 C 6.0 1.4318690773 0.3593712188-1.4473206893 S23
H 1.0-1.3698305884 1.7953693773-0.5936743502 H 1.0 2.6192446183-0.8527499158-2.7963181639 C 6.0 0.5368758166 1.4811239939 1.4095936667 C 6.0 3.9515166513-0.1173244835-1.2711510461 C 6.0 2.7447056407 0.0560993311-2.2125043032 H 1.0 2.5862423710 0.9857343304 0.9386202085 8.0 0.6965779374 2.6890247025 1.3952425960 H 1.0 1.3659451360 1.4258156339-1.2472082345 H 1.0 4.1113166925 0.8077084562-0.7228216714 H 1.0 4.8489199804-0.2947972025-1.8589193801 H 1.0 2.9369653842 0.8636071078-2.9156115761 H 1.0-3.6523361303 1.8571278294 1.1333160975 H 1.0-5.0691123704 1.0465003519 0.5118449456 TTAL ENERGY = -776.5866658799 nitroxide 5 CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z ------------------------------------------------------------ H 1.0-3.3524852532-0.8650679857-0.2273774852 H 1.0-2.6807335557 0.2415957836 2.5371592272 H 1.0-2.2424569312-1.3648449394 1.9916825976 C 6.0-3.5992448399-0.3093120299 0.6733505603 C 6.0-2.4173423004-0.3446836698 1.6600930390 H 1.0-4.4732922916-0.7726961046 1.1248911292 8.0-4.5708896903 1.1483308964-1.0495562119 8.0-0.9992870470-1.6665472797-0.4023766138 H 1.0 1.5237221499-2.8098395255 0.9445506026 H 1.0-2.8288856522 2.8531219143-0.4787626467 H 1.0 1.1382320434-2.7788099124-0.7621315783 C 6.0-3.9604552011 1.1561383344 0.2697798625 H 1.0-0.2393984102 0.2091976734 3.0506045230 N 7.0-0.2946368443-0.9660548713 0.5437141766 C 6.0-1.0864439874 0.2188253246 1.0553764469 C 6.0 1.7053996633-2.2751713746 0.0158104410 C 6.0-2.6894970784 2.0673030117 0.2599655149 8.0-4.9260498066 1.7040155100 1.2085922997 C 6.0-6.0548476140 1.9924162576 0.4171453542 S24
C 6.0-5.8556768382 1.6861118097-0.8410333050 H 1.0 3.4587309029-3.3116478387-0.7127782543 C 6.0-0.2694261138 0.8854892972 2.1989711855 H 1.0-2.6021587406 2.5417980885 1.2342895760 C 6.0-1.4178465110 1.2602739167-0.0653536846 C 6.0 1.1625125560-0.8218629181 0.1544255331 H 1.0 1.9713291261-0.7717834758 2.1668584307 H 1.0-0.7550799233 1.8057677320 2.5106360027 C 6.0 3.2127291539-2.3275938571-0.3201825845 H 1.0-1.5753509197 0.7383880117-1.0051408384 H 1.0 3.8082078687-2.1743615282 0.5762794873 H 1.0 1.9458504996-1.5513302334-2.6768027606 C 6.0 1.9141110542-0.1012528957 1.3121855358 H 1.0 0.4181961106-0.0152262173-1.7373549692 H 1.0-0.5819957921 1.9407599529-0.2029738722 C 6.0 1.1745785796 1.1726501600 1.7534142158 C 6.0 1.3629400179-0.0569633496-1.2045267685 C 6.0 2.3978820194-0.7171225723-2.1465157725 C 6.0 3.6396512147-1.2600845427-1.3834201588 8.0 1.6715122141 2.2851296406 1.7462553318 H 1.0 2.9228942583 0.1450274098 0.9947972438 C 6.0 5.6004796041-0.1335064307-1.3362362019 C 6.0 5.7286217409-1.0833482782-2.2293735699 8.0 4.5602440190-1.8627149500-2.3333050067 H 1.0 1.6664602681 0.9665963432-1.0023355743 8.0 4.3282417607-0.1577466105-0.7319645038 H 1.0 2.7250457059 0.0059898098-2.8900944249 H 1.0-6.9161071526 2.4153784264 0.9150829760 H 1.0-6.5014461084 1.7786698774-1.7030193616 H 1.0 6.2925395295 0.6288909135-1.0067630102 H 1.0 6.5609265423-1.3482877040-2.8665361354 TTAL ENERGY = -1221.5632368278 nitroxide 6 CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z ------------------------------------------------------------ H 1.0-4.5653861613-0.6886913483 1.1203125325 S25
H 1.0-2.0711189130-1.5401132211 1.8511229995 C 6.0-3.6623926921-0.1253662970 1.3851219969 H 1.0-3.6839766093 0.0419683771 2.4651266782 C 6.0-2.4072067242-0.9606681746 0.9961932511 H 1.0-2.6578437281-1.6605974864 0.2040219968 H 1.0-0.6764092050 0.3356078212 2.5480974418 8.0-3.6965978276 1.1804467648 0.7822680287 H 1.0-1.5720810950 1.6585154506 1.7955833108 H 1.0 2.2018645443-2.1403006078 0.8122000815 C 6.0-0.8036192168 0.9087763050 1.6322556277 C 6.0-1.2506979325-0.0510890593 0.4926231193 H 1.0 1.8132604607-0.0142000698 1.9428977616 H 1.0 1.9292341065-2.3047002650-0.9112758734 N 7.0-0.0992108903-0.9731130002 0.1539733806 C 6.0 2.2543803970-1.6153131131-0.1371457711 C 6.0-3.2954998686 1.0793718779-0.5918674904 H 1.0-3.8889360319 0.3200145917-1.1133736029 8.0-0.4603585801-1.8905593609-0.8015855522 8.0 0.6919741442 2.7905568739 1.2339651722 C 6.0 0.5371283941 1.5836769164 1.2943171746 C 6.0-1.7783235274 0.7564277306-0.7396108805 H 1.0-1.2161142555 1.6788617987-0.8475475569 C 6.0 1.6584805741 0.5628975665 1.0337999190 H 1.0 4.2241677749-1.9231688897-1.0158280405 C 6.0 1.2766930262-0.4060353879-0.1217847919 H 1.0-3.5148012409 2.0446120219-1.0551795790 C 6.0 3.7188905678-1.1618528739-0.4092231255 H 1.0 4.2673633863-1.0740521447 0.5322259913 H 1.0 2.5834909950 1.0747845010 0.7854975764 H 1.0-1.6362521905 0.1719733088-1.6442283363 H 1.0 2.9014270153-0.6347818435-2.7641866643 C 6.0 1.3820313057 0.3126655189-1.5078620251 8.0 3.8163387576 0.1251031078-1.0448305228 H 1.0 0.7003397956-0.1556499639-2.2121756063 C 6.0 2.8279259055 0.2187951217-2.0809580051 H 1.0 1.0941609893 1.3547440848-1.4086975512 H 1.0 3.0576645503 1.1204513678-2.6542350651 TTAL ENERGY = -847.1014791492 S26
nitroxide 7a CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z ------------------------------------------------------------ H 1.0 2.0031364586-2.4549034032 0.8750073135 H 1.0 4.2192820775-2.3679535999-0.5504300278 H 1.0-2.1911207318-1.7706365446 1.7094765841 H 1.0 1.8978854094-2.5625308253-0.8699057502 H 1.0 4.0554299418-1.3054930311 0.8433308760 C 6.0 2.1652772412-1.9044612695-0.0477572000 C 6.0 3.6619615405-1.5141774435-0.1518952130 H 1.0 1.6822068893-0.2818045028 1.9992153013 H 1.0-2.7833404883-1.7985362035 0.0613739059 H 1.0-4.6374252004-0.9228154278 1.2122600472 C 6.0-2.5091961192-1.1417917347 0.8823188868 H 1.0-0.8248677535 0.1268004124 2.4982546987 8.0-0.5170495052-2.1115891179-0.8343646752 H 1.0-3.6481682588-0.0485071550 2.3766163058 N 7.0-0.1756014510-1.1978540462 0.1321376215 C 6.0-3.7392259641-0.3065521892 1.3212079091 C 6.0 1.2252700239-0.6656730073-0.0867476441 N 7.0 3.8285065314-0.3064327021-0.9946226129 C 6.0 5.1606026063 0.1150695564-1.3487187812 C 6.0 6.2580650351-0.1969380519-0.3100229307 8.0 5.3785601513 0.7412867564-2.3723625124 C 6.0 1.5780464248 0.2962876587 1.0834404176 H 1.0 2.8102046528-1.0815988311-2.6954654010 C 6.0-1.3212477328-0.2501969947 0.4201749277 C 6.0-0.8989216141 0.7002647878 1.5766283325 H 1.0 2.5218921674 0.7895216915 0.8733832868 C 6.0 2.8190541978-0.1864089287-2.0663287527 H 1.0-1.6531042607 1.4702950415 1.7048930151 C 6.0 0.4705077554 1.3422063382 1.2963867420 8.0 0.6566832270 2.5451805311 1.2465414239 C 6.0 1.4055869667 0.0472848810-1.4702994594 H 1.0-3.8099541546-0.0021519319-1.3774580507 N 7.0-3.8302261285 0.9430783121 0.5295236772 C 6.0-5.0002265458 1.7725819889 0.6731629524 C 6.0-5.6696960086 1.7483352099 2.0630093209 S27
8.0-5.3815263049 2.4964392914-0.2312692358 H 1.0 0.6767938384-0.3400060967-2.1761757497 H 1.0 3.1037368749 0.6530270423-2.6987918938 C 6.0-1.7773656684 0.5672353357-0.8363892475 C 6.0-3.3093735139 0.8132428520-0.8466256664 H 1.0 1.2255461974 1.1128111389-1.3605361672 H 1.0-1.5204677782 0.0201417479-1.7386956799 H 1.0-1.2532118005 1.5181370574-0.8660474794 H 1.0-3.5383374636 1.7361101466-1.3773154686 H 1.0 6.4325210646-1.2660412823-0.2366366263 H 1.0 5.9729492921 0.1770034884 0.6685614105 H 1.0 7.1776272492 0.2872678327-0.6215406915 H 1.0-4.9398384344 1.9513393707 2.8406726272 H 1.0-6.1266680994 0.7830488112 2.2585246496 H 1.0-6.4398198342 2.5120140399 2.0901506836 TTAL ENERGY = -1107.7035633451 nitroxide 7b CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z ------------------------------------------------------------ H 1.0 2.6375675731-0.3469874248 1.8357219344 H 1.0 0.1045135359-0.0245708098 2.2628774416 8.0 1.5674959541 2.5050026668 1.2405538559 H 1.0 3.1184935462-2.3971127120 0.5745509323 H 1.0-1.1419491314-1.9097992569 1.3269040835 C 6.0 2.5567705627 0.2951482520 0.9612719438 C 6.0 0.0515726587 0.6016335333 1.3746727758 H 1.0-0.7289746908 1.3424517148 1.5186288232 H 1.0 3.4986310374 0.8219657809 0.8342349345 C 6.0 1.4134044132 1.2972391933 1.1985645651 H 1.0-2.6940694021-0.2756131150 2.0196691625 H 1.0 4.2855340608-1.4174182374-0.3161280990 C 6.0 3.2624845547-1.7801086835-0.3063545558 C 6.0-1.4607982283-1.2547019175 0.5207371460 H 1.0-3.6040739246-1.1636365059 0.8024686218 C 6.0-2.7446367854-0.5028490368 0.9543011954 C 6.0 2.2746151944-0.5829773123-0.2903752856 S28
C 6.0-0.2995894963-0.2886838898 0.1473804789 C 6.0-4.8328289439 1.3971830454 1.6777065648 H 1.0 3.1013828544-2.3916027268-1.1879540618 N 7.0 0.8877779358-1.1743170291-0.1643107512 H 1.0-1.6740422548-1.8807980862-0.3411588432 N 7.0-2.8852972282 0.7644532666 0.1993534194 H 1.0-0.3125456475 1.5788598316-0.9925976822 H 1.0 1.9086101348 1.1751791820-1.5648791883 C 6.0-4.1075994699 1.5168421377 0.3210835495 C 6.0 2.4732787049 0.2505583162-1.5885531457 8.0 0.6145603257-2.0272813954-1.2050953228 C 6.0-0.7526710318 0.5890697321-1.0706669836 C 6.0-2.2954232816 0.7188758730-1.1538141478 H 1.0-0.3986856534 0.1410335695-1.9950981369 H 1.0 2.1676345474-0.3244722474-2.4567335571 8.0-4.4931068293 2.2532109238-0.5715573993 H 1.0-2.7076225143-0.1126717608-1.7331761596 H 1.0-2.5672413831 1.6401775071-1.6667867793 H 1.0 3.5233907951 0.5007599370-1.6980645050 H 1.0-4.1504502461 1.6124801385 2.4942307876 H 1.0-5.2369132785 0.3990402363 1.8165414684 H 1.0-5.6492809678 2.1112943096 1.6988939204 TTAL ENERGY = -827.5615253750 nitroxide 8a CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z ------------------------------------------------------------ 8.0 5.2497876264-1.1406185294-1.6500762578 8.0 2.3259479707-3.6515975107-1.7626136021 H 1.0 2.8392505079-0.3964769529-3.2150338865 S 16.0 3.3759345216-1.9268487608-1.4534510074 H 1.0 3.1094858668-2.4943668197 0.8545482642 C 6.0 2.3175159187-0.6493155401-2.2950960089 H 1.0 3.7192221835-0.8423935623 0.6815972094 C 6.0 2.9795311978-1.5548632853 0.3227876524 H 1.0 1.3658423867-1.1165190106-2.5362543337 H 1.0 3.1334970056 0.9665482695-1.1432366356 S29
C 6.0 2.1454999378 0.6003781406-1.4126996258 H 1.0 1.6615696655 1.3736055634-2.0052231815 H 1.0 1.8036275179 2.4379027789 0.4040441475 C 6.0 1.5370285086-1.0408871178 0.4866211502 H 1.0 0.8645346906-1.7506148353 0.0105324811 C 6.0 1.3043393192 0.3908584001-0.1074852153 H 1.0 1.3148034985-1.0353335251 1.5504184460 C 6.0 1.7434871953 1.4791548512 0.9144025321 H 1.0 2.7280670652 1.2392550654 1.3057504033 8.0-0.5461631511-0.2053081898-1.4854738243 N 7.0-0.1442412781 0.6275380568-0.4793590259 H 1.0-3.1010151906 1.9278596366 0.6235626672 C 6.0 0.7286203593 1.6032546488 2.0632360322 8.0 1.0067657509 1.4352546364 3.2367433919 H 1.0-2.1058229734 2.3483091144-0.7651427802 C 6.0-2.4544041299 1.5205049551-0.1507916162 C 6.0-1.2149408575 0.8813986184 0.5593504255 C 6.0-0.6768635342 1.9576633372 1.5513074026 H 1.0-4.1761843413 1.1389681665-1.4143478892 C 6.0-3.3074805675 0.5990735312-1.0452708254 H 1.0-1.3663293279 2.0611354627 2.3842024374 H 1.0-0.6184541389 2.9131277847 1.0346715014 H 1.0-0.7968415903-0.8131800413 1.8840550400 H 1.0-2.7467761305 0.2029153634-1.8874113168 C 6.0-1.6534839207-0.3762492363 1.3804463091 H 1.0-2.3457550034-0.0390903295 2.1487813311 S 16.0-3.9731110718-0.8495469720-0.0954688936 C 6.0-2.3614959302-1.4795565017 0.5723923755 H 1.0-2.6103367909-2.3203384229 1.2153270948 H 1.0-1.7743780515-1.8393363891-0.2692443769 8.0-4.7979262471 0.0250974033 1.5384382201 8.0-4.4823574675-2.2073632519-1.5495372120 TTAL ENERGY = -1780.5730910068 nitroxide 8b CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z ------------------------------------------------------------ S30
8.0 3.9439432819 1.3836207910-1.3425567712 H 1.0 1.3047390624 0.7976282655-3.0857487155 S 16.0 3.0117847366-0.3429970067-1.8529395282 8.0 3.2822419502-1.8942389553-3.1624216598 H 1.0 1.4858631013 1.9153031331-0.8793297132 C 6.0 1.2719460365 0.2216857862-2.1641310667 H 1.0 3.7170379850-1.4540644662 0.1473858489 C 6.0 2.7318408045-1.1695279996-0.2143233374 C 6.0 0.7785068681 1.0975086532-0.9980798121 H 1.0 2.1446659316-2.0643325913-0.4011855653 H 1.0-0.1765787528 1.5320233516-1.2753857063 H 1.0 0.6613542548-0.6643689943-2.3203325194 H 1.0 0.9442874361 2.2953533866 1.3630572077 C 6.0 0.6613248263 0.3705409777 0.3824466585 C 6.0 0.2969132358 1.4293446799 1.4679033738 C 6.0 2.0506292771-0.2212378611 0.7923744893 H 1.0-2.1800784412 0.9815715384-1.1475696874 C 6.0-1.1795314980 1.8527667825 1.3763727307 H 1.0 1.9275014562-0.7656882422 1.7264806560 8.0-1.5475369743 2.9967675152 1.1790750901 H 1.0 2.7238857168 0.6131500552 0.9775119737 H 1.0 0.4638138363 0.9945367449 2.4508952389 C 6.0-2.4501408751-0.0319759190-0.8752063715 N 7.0-0.3695257468-0.7332054318 0.4454751079 8.0-0.1019506753-1.7796486664-0.3929554819 H 1.0-3.5327844256-0.0856590162-0.8287235290 C 6.0-1.8552613534-0.4454184231 0.5024434421 C 6.0-2.1307471390 0.6590405226 1.5618578706 H 1.0-3.1649388992 0.9838147202 1.4871360688 H 1.0-1.9715695271 0.2478745161 2.5563477180 C 6.0-2.5340752014-1.7649855954 0.9607553957 H 1.0-2.4023653861-2.5394172222 0.2124579044 H 1.0-2.0988860307-2.1060940884 1.8944134952 H 1.0-3.5967439504-1.6011630334 1.1090448407 H 1.0-2.1095679211-0.7085069069-1.6525456462 TTAL ENERGY = -1163.9971017843 nitroxide 8c S31
CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z ------------------------------------------------------------ H 1.0-3.8301997859-2.0069915477 0.4073730634 H 1.0-4.1602813868-1.9837436869-1.3156039548 C 6.0-3.3910494160-1.8206241980-0.5664600854 H 1.0-3.7086753157 0.3006686699-0.4772046110 H 1.0-1.8462905991-1.8002958157 3.2784788959 H 1.0-2.5736713833-0.1883129956-1.7128205738 H 1.0-2.5945992610-2.5360570369-0.7367852229 C 6.0-2.8787489645-0.3716302161-0.6849393994 H 1.0-1.9257872392-2.4623904292 1.6514227323 C 6.0-1.5281852861-1.6520222544 2.2504096192 H 1.0 1.0830121477 0.0146201580-2.3255046334 H 1.0-0.4459943734-1.7098243925 2.2179303921 H 1.0 0.3981433015 1.5404597612-1.7909067790 H 1.0 2.6783858266 2.2945985202-1.0168846757 C 6.0-1.7028185153 0.0646497203 0.2535564117 H 1.0-3.0931953783-0.2016987361 1.8958714245 H 1.0-1.5975109959 1.8953949016-0.9300598231 C 6.0-2.0171214804-0.2764749458 1.7561951105 C 6.0 1.1598326799 0.7969880975-1.5738576940 8.0 5.5088648484 1.4991618595-1.0385238903 C 6.0 2.5301010219 1.4850141349-1.7279250421 C 6.0-1.5954215300 1.6146022866 0.1211379251 N 7.0-0.4143999287-0.5966984055-0.1830165426 H 1.0 2.6391754508 1.8835449904-2.7336858453 C 6.0-0.3292177639 2.1966207166 0.7874203153 8.0-0.5107385008-1.4582366686-1.2318989250 C 6.0 0.8951750927 0.1511492262-0.1726738671 H 1.0-1.5737974528 0.4854513649 2.3923175298 H 1.0 3.6066875628 0.3493064314 0.8844770109 8.0-0.2546684388 3.3578473028 1.1481955187 S 16.0 3.9292948688 0.2871217968-1.5082709306 H 1.0-2.4714063383 2.0735354150 0.5727036278 C 6.0 0.8427488698 1.2056330623 0.9629041953 H 1.0 1.8953111711-1.7112779644-0.6307954118 H 1.0 1.7703971525 1.7665301749 1.0162530930 C 6.0 3.4364300618-0.4204208129 0.1351007251 S32
C 6.0 1.9827614044-0.9301821004 0.1212056229 8.0 3.4632033079-1.2048669254-2.8188434625 H 1.0 0.7247242492 0.6884779179 1.9125749558 H 1.0 1.7760403987-1.3769344424 1.0911490113 H 1.0 4.1234879175-1.2426959346 0.3199821894 TTAL ENERGY = -1241.1438605270 S33