SUPPORTING INFORMATION ********************** Andrzej Marcinek, Jan Adamus, Krzysztof Huben, Jerzy Gebicki, Tadeusz Bartczak, Pawel Bednarek, Thomas Bally Hydrogen Transferred Radical Cations of NADH Model Compounds. I: Spontaneous Tautomerization Journal of American Chemical Society Crystal structure of 1-methyl-1,4-dihydro-6,7,8,9-tetrahydro-5H- cyclohepta[b]pyridin-5-one (1HK): X Y Z 6 0.000000 0.000000 0.000000 6 0.000000 0.000000 2.506300 6 0.695060 0.000000 3.843777 6 0.690235 0.070477 1.333109 6 -1.392726 -0.586020 0.096917 6 2.146838 0.247106 3.691595 1 -3.133687 -0.294598 1.338672 6 2.819732 0.292527 0.062855 6 -2.171756 0.064344 1.216178 7 2.052361 0.223274 1.307946 8 -2.060932 -0.090343 3.580641 6 2.737971 0.342044 2.520682 6 -1.439763 -0.030115 2.519797 1 3.751625 0.396258 0.268807 1 2.521718 1.044752 -0.454926 1 2.690971 -0.513523 -0.441091 1 3.684405 0.499938 2.497248 1 2.679749 0.344992 4.483712 1 0.198675 0.740004 4.436141 1 0.497377 -0.792064 4.338954 1 -2.261852 1.117729 1.028842 1 -1.854134 -0.441714 -0.733162 1 -1.340053 -1.532437 0.245783 Crystal structure of 1-methyl-1,4,7,8-tetrahydro-5(6H)-quinolinone (2HK): X Y Z 6 0.000000 0.000000 0.000000 6 0.000000 0.000000 2.497400 6 2.177997 0.000000 1.291607 1 -0.683146 0.657636 -0.072298 7 2.887347 0.134511 0.107921 6 2.988024 -0.249238 2.532875 6 4.301582 0.511013 0.083339 8 -1.228886 -0.117030 2.394825 1 3.513076 1.620971 3.188589 6 3.010493 0.887749 3.550016 6 2.199552 0.105302 -1.104119 1 1.645216 1.745109 4.796770 6 0.887567 0.016809 -1.201949 6 1.618973 1.370789 3.913796 1 0.490303 -0.040292 -2.074027 1 -0.170534 0.538243 4.453546 6 0.552934 0.280858 3.877731 1 4.597894 0.547298 -0.829592 1 4.819147 -0.140857 0.561460 1 4.415472 1.372667 0.490757 1 2.710438 0.155452 -1.915814 1 -0.512203 -0.771220 -0.012604 1 0.929552 -0.529692 4.227839 1 1.366759 2.071264 3.307725 1 3.457965 0.589260 4.346017 1 3.892078 -0.438831 2.273296 1 2.642748 -1.033808 2.966227 6 0.808036 -0.016326 1.281019 Total energies, thermal corrections, and cartesian coordinates of all stationary points located in this study, ordered by method ( B3LYP all with the 6-31G* basis set) 1-methyl-1,4-dihydro-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridin-5-one; neutral form (1HK): HF=-558.1489602 X Y Z 6 2.120979 1.788967 .422115 6 .701064 2.119903 .060768 6 -.112077 .851100 -.162083 6 .474430 -.384491 -.289033 7 1.834039 -.556862 -.066125 6 2.604664 .547592 .342574 6 -1.560666 1.095437 -.254871 6 -2.607027 -.018225 -.091848 6 -2.225239 -1.113123 .920066 6 -1.274646 -2.175015 .340441 6 -.315947 -1.604942 -.724321 6 2.502997 -1.845075 -.206180 1 .657040 2.763130 -.833860 1 2.782495 2.583097 .756432 1 3.631356 .307836 .596448 1 2.540940 -2.186063 -1.248791 1 3.531006 -1.736754 .143909 1 2.027077 -2.623207 .400684 1 -.901640 -1.324713 -1.604650 1 .350049 -2.399087 -1.065541 1 -1.855342 -2.971637 -.143038 1 -.704266 -2.650816 1.148335 1 -3.133611 -1.606036 1.286988 1 -1.762788 -.634933 1.791609 1 -2.840171 -.462260 -1.071087 1 -3.516174 .501246 .225279 8 -1.965112 2.254945 -.363820 1 .225454 2.725903 .844951 1-methyl-1,4-dihydro-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridin-5-one;keto radical cation (1HK.+): HF=-557.9068666 ZPE=152.63322 (Kcal/Mol) Zero-point correction= .243236 (Hartree/Particle) Thermal correction to Energy= .254946 Thermal correction to Enthalpy= .255890 Thermal correction to Gibbs Free Energy= .205099 X Y Z 6 2.125327 1.792841 .420962 6 .676953 2.048529 .270324 6 -.116264 .832707 -.079932 6 .477858 -.404469 -.276874 7 1.839981 -.534521 -.075254 6 2.636694 .550303 .258032 6 -1.594120 1.089015 -.288832 6 -2.639725 .023024 .011733 6 -2.185840 -1.085744 .974520 6 -1.303603 -2.158642 .314690 6 -.327127 -1.593361 -.746966 6 2.512125 -1.842292 -.225659 1 .478557 2.829926 -.487184 1 2.792290 2.609630 .676629 1 3.690805 .333495 .373329 1 2.539424 -2.134726 -1.279062 1 3.531800 -1.753816 .145893 1 1.988107 -2.601783 .356588 1 -.904354 -1.261630 -1.616678 1 .315499 -2.392639 -1.116267 1 -1.929832 -2.893362 -.203775 1 -.748925 -2.708879 1.083532 1 -3.070061 -1.569698 1.400818 1 -1.658702 -.631634 1.823423 1 -2.990449 -.398610 -.941761 1 -3.496240 .571233 .417544 8 -1.908158 2.214155 -.635552 1 .273812 2.519436 1.186181 1-methyl-1,4-dihydro-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridin-5-one; neutral enol form (1HE) HF=-558.0966798 X Y Z 6 2.010232 1.943608 -0.238990 6 0.677300 2.073354 0.032055 6 -0.190815 0.893676 0.085691 6 0.543820 -0.365589 0.248980 7 1.854365 -0.422653 -0.053621 6 2.608635 0.678089 -0.371804 6 -1.556155 0.955068 0.110853 6 -2.560659 -0.149470 -0.107873 6 -2.027545 -1.371164 -0.876110 6 -1.125668 -2.302151 -0.047230 6 -0.159635 -1.536701 0.881545 8 -2.206921 2.193391 0.203288 6 2.583745 -1.699616 0.043577 1 2.636866 2.823357 -0.356608 1 0.248076 3.063729 0.148089 1 -1.715319 2.752626 0.823360 1 3.641583 0.508780 -0.634116 1 -3.371701 0.303308 -0.695755 1 -3.043352 -0.472505 0.831719 1 -1.474862 -1.006860 -1.751057 1 -2.872387 -1.954649 -1.263451 1 -0.560370 -2.956795 -0.725304 1 -1.738707 -2.964902 0.579304 1 0.535617 -2.242947 1.347071 1 -0.753581 -1.110076 1.700244 1 1.983949 -2.512076 -0.367300 1 3.502547 -1.613762 -0.535825 1 2.836929 -1.920414 1.084505 1-methyl-1,4-dihydro-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridin-5-one; enol radical cation (1HE.+): HF=-557.9248794\S2=0.77 6 -1.981764 1.946067 .379047 6 -.615489 2.037007 .195009 6 .158027 .871640 -.098576 6 -.545968 -.366229 -.269526 7 -1.879038 -.403657 -.042563 6 -2.606160 .712787 .282523 6 1.573145 .937937 -.225008 6 2.570041 -.159873 .028046 6 2.069924 -1.293276 .938026 6 1.106750 -2.270325 .242390 6 .173590 -1.584271 -.784063 8 2.184748 2.123048 -.421266 6 -2.637029 -1.675626 -.174247 1 -2.574313 2.818867 .629400 1 -.125885 2.994261 .342544 1 1.580386 2.793646 -.782376 1 -3.664509 .568610 .446984 1 3.432760 .334165 .491420 1 2.950842 -.557958 -.925696 1 1.593965 -.851458 1.822034 1 2.934903 -1.852195 1.308578 1 .516817 -2.808696 .993111 1 1.672208 -3.027954 -.311975 1 -.521293 -2.316433 -1.196633 1 .782921 -1.244374 -1.629081 1 -2.129090 -2.470397 .371209 1 -3.626639 -1.529489 .254861 1 -2.738188 -1.944406 -1.228030 1-methyl-1,4,7-tetrahydro-5(6H)-quinolinone; neutral form (2HK): HF=-518.8509106 X Y Z 6 1.756249 1.959105 .067714 6 2.403403 .793263 -.009493 6 .256677 2.049369 .113179 6 -.369160 .668754 .017534 6 .367631 -.486505 -.030869 7 1.751725 -.454106 -.058098 6 -1.828279 .645784 -.072562 6 -2.523303 -.700961 -.244216 6 -1.732967 -1.827049 .419571 6 -.287248 -1.851157 -.087694 8 -2.480527 1.689675 -.049256 6 2.564185 -1.663634 -.059754 1 2.341584 2.874055 .087776 1 3.485794 .732504 -.046842 1 -.127286 2.684681 -.699637 1 -.084759 2.555991 1.030082 1 -2.623183 -.896689 -1.323231 1 -3.537857 -.612209 .156222 1 -2.203324 -2.800296 .236646 1 -1.726547 -1.674565 1.506848 1 -.262563 -2.220252 -1.125691 1 .290550 -2.570457 .502720 1 2.229845 -2.370550 -.824924 1 3.594635 -1.388463 -.292883 1 2.562123 -2.174214 .913184 1-methyl-1,4,7-tetrahydro-5(6H)-quinolinone; keto radical cation (2HK.+): HF=-518.6040903\S2=0.775 X Y Z 6 1.759878 1.955719 .090763 6 2.421020 .772622 .031417 6 .282264 2.010999 .070439 6 -.361471 .668470 -.002528 6 .370028 -.505061 -.028812 7 1.752350 -.437269 -.035079 6 -1.860064 .652132 -.080681 6 -2.543028 -.687978 -.241452 6 -1.746473 -1.808288 .434449 6 -.295686 -1.860385 -.072128 8 -2.450385 1.717307 -.042295 6 2.563303 -1.668630 -.106165 1 2.332437 2.875930 .146040 1 3.501760 .707204 .032817 1 -.075567 2.645777 -.761042 1 -.104280 2.563792 .947003 1 -2.638633 -.883949 -1.320645 1 -3.558997 -.603834 .153610 1 -2.220968 -2.776409 .251656 1 -1.743739 -1.657537 1.520971 1 -.272396 -2.230299 -1.109144 1 .271940 -2.581063 .524266 1 2.203304 -2.305105 -.916189 1 3.600064 -1.397041 -.298459 1 2.503088 -2.212645 .841215 1-methyl-1,4,7-tetrahydro-5(6H)-quinolinone; neutral enol form (2HE): HF=-518.7939902 X Y Z 6 1.592088 2.061757 .146872 6 2.410508 .926148 .033277 6 .228791 1.966056 .144332 6 -.429258 .663386 .007335 6 .467432 -.481604 -.047358 7 1.797098 -.306716 -.046038 6 2.690686 -1.475018 -.127790 6 -1.780489 .486547 -.094574 6 -2.462772 -.844775 -.093699 6 -1.529613 -1.918623 .476912 6 -.136618 -1.858056 -.176215 8 -2.663486 1.565220 -.138362 1 2.074825 3.029556 .253728 1 3.488736 .939093 .029710 1 -2.239901 2.282614 -.636387 1 -.380127 2.852263 .293707 1 2.413038 -2.109528 -.971673 1 3.710337 -1.121786 -.273377 1 2.641545 -2.059637 .794689 1 -2.805810 -1.134239 -1.103105 1 -3.374504 -.782475 .517757 1 -1.951248 -2.919931 .331994 1 -1.420240 -1.766359 1.557932 1 -.237369 -2.111284 -1.245440 1 .504395 -2.627942 .265068 1-methyl-1,4,7-tetrahydro-5(6H)-quinolinone; enol radical cation (2HE.+): HF=-518.6223629\S2=0.772 X Y Z 6 1.617337 2.059000 .143467 6 2.391927 .913332 .046099 6 .239929 1.962144 .125733 6 -.392343 .682416 .004517 6 .450142 -.474998 -.050093 7 1.789563 -.320111 -.044926 6 2.684564 -1.500846 -.139342 6 -1.790632 .509154 -.087165 6 -2.459336 -.826843 -.117354 6 -1.554783 -1.907492 .476382 6 -.149208 -1.855788 -.141706 8 -2.651127 1.532224 -.159907 1 2.111031 3.020159 .233420 1 3.472352 .923078 .043477 1 -2.210270 2.391740 -.265547 1 -.348759 2.868781 .227765 1 2.388977 -2.127015 -.981676 1 3.702466 -1.149775 -.298388 1 2.642452 -2.076116 .788144 1 -2.727377 -1.069752 -1.157739 1 -3.406547 -.753439 .428511 1 -1.984117 -2.898339 .306294 1 -1.478561 -1.771922 1.561569 1 -.198272 -2.143639 -1.204113 1 .493124 -2.591254 .348787 1-methyl-3-formyl-1,4-dihydropyridine; neutral form (3HK): State 1-A'\HF=-402.1025306 ZPE=93.57220 (Kcal/Mol) Zero-point correction= 0.149117 (Hartree/Particle) Thermal correction to Energy= 0.157009 Thermal correction to Enthalpy= 0.157953 Thermal correction to Gibbs Free Energy= 0.116245 X Y Z 6 1.671161 -0.932898 0.000000 6 0.654288 -1.803181 0.000000 7 -0.694169 -1.399483 0.000000 6 -0.961255 -0.060639 0.000000 6 0.000000 0.902124 0.000000 6 1.478199 0.565345 0.000000 6 -0.410626 2.291769 0.000000 6 -1.743140 -2.404998 0.000000 8 0.362991 3.241528 0.000000 1 2.683456 -1.326863 0.000000 1 0.800743 -2.878283 0.000000 1 -2.014965 0.207899 0.000000 1 1.972626 1.026276 0.869614 1 -1.513765 2.459713 0.000000 1 -1.680294 -3.042899 0.890741 1 -2.716640 -1.910192 0.000000 1 -1.680294 -3.042899 -0.890741 1 1.972626 1.026276 -0.869614 1-methyl-3-formyl-1,4-dihydropyridine; keto radical cation (3HK.+): State=2-A"\HF=-401.8426859\S2=0.775928 ZPE=93.02687 (Kcal/Mol) Zero-point correction= 0.148248 (Hartree/Particle) Thermal correction to Energy= 0.156960 Thermal correction to Enthalpy= 0.157904 Thermal correction to Gibbs Free Energy= 0.113247 X Y Z 6 1.640881 -0.958034 0.000000 6 0.595451 -1.827845 0.000000 7 -0.711562 -1.378540 0.000000 6 -0.991704 -0.041017 0.000000 6 0.000000 0.905374 0.000000 6 1.438684 0.513264 0.000000 6 -0.348223 2.350236 0.000000 6 -1.799261 -2.376586 0.000000 8 0.517068 3.199653 0.000000 1 2.651278 -1.354402 0.000000 1 0.718606 -2.904446 0.000000 1 -2.043470 0.225322 0.000000 1 1.959393 0.979731 0.857185 1 -1.426335 2.600196 0.000000 1 -1.714373 -3.000560 0.893944 1 -2.760698 -1.864804 0.000000 1 -1.714373 -3.000560 -0.893944 1 1.959393 0.979731 -0.857185 1-methyl-3-formyl-1,4-dihydropyridine; neutral enol form (3HE): HF=-402.0461046 ZPE=92.28165 (Kcal/Mol) Zero-point correction= .147060 (Hartree/Particle) Thermal correction to Energy= .155733 Thermal correction to Enthalpy= .156677 Thermal correction to Gibbs Free Energy= .112728 X Y Z 6 -1.389505 0.422099 0.000000 7 0.658541 -1.431820 0.000000 6 0.000000 0.916036 0.000000 6 -1.658138 -0.917021 0.000000 6 -0.636118 -1.889891 0.000000 6 0.983339 -0.140454 0.000000 6 0.395040 2.218606 0.000000 8 -0.440547 3.321478 0.000000 1 -2.216103 1.127687 0.000000 1 -1.359938 3.016586 0.000000 1 -2.688156 -1.263351 0.000000 1 -0.782032 -2.959031 0.000000 1 2.043030 0.087405 0.000000 6 1.725727 -2.440986 0.000000 1 2.699632 -1.951880 0.000000 1 1.629720 -3.067573 0.890931 1 1.629720 -3.067573 -0.890931 1 1.436661 2.518309 0.000000 1-methyl-3-formyl-1,4-dihydropyridine; enol radical cation (3HE.+): State=2-A"\HF=-401.8630418\S2=0.774 ZPE= 94.33526 (Kcal/Mol) Zero-point correction= .150333 (Hartree/Particle) Thermal correction to Energy= .158862 Thermal correction to Enthalpy= .159806 Thermal correction to Gibbs Free Energy= .116321 X Y Z 6 -1.376439 .481729 .000000 7 .606869 -1.448589 .000000 6 .000000 .880810 .000000 6 -1.704467 -.862341 .000000 6 -.707968 -1.833442 .000000 6 .960272 -.161034 .000000 6 .470501 2.205802 .000000 8 -.269310 3.309300 .000000 1 -2.173464 1.218764 .000000 1 -1.225891 3.132352 .000000 1 -2.741145 -1.180489 .000000 1 -.900095 -2.898003 .000000 1 2.023538 .049189 .000000 6 1.643905 -2.509725 .000000 1 2.631322 -2.050118 .000000 1 1.522902 -3.123625 .894754 1 1.522902 -3.123625 -.894754 1 1.531505 2.430493 .000000