The Rearrangements of Naphthylnitrenes: UV/Vis and IR Spectra of Novel Azirines, Cyclic Ketenimines and Nitrile Ylides by Alexander Maltsev, Thomas Bally,* Meng-Lin Tsao, Matthew S. Platz*, Arvid Kuhn, Michael Vosswinkel, and Curt Wentrup* SUPPORTING INFORMATION *********************** ==================================== A. CASSSCF (12,12)/6-31G* geometries ==================================== Singlet 1-naphthylnitrene. CASSCF(12,12)/6-31G* -437.278588 CASPT2(12,12)/6-31G* -438.541359 reference weight 0.7009 ZPE 90.64 N -1.700435 2.150643 0.000000 C 2.721939 -0.371184 0.000000 C 1.695645 -1.307254 0.000000 C 0.344902 -0.901603 0.000000 C 0.051130 0.485270 0.000000 C 1.091868 1.416390 0.000000 C 2.422276 0.995147 0.000000 C -2.417144 -0.121020 0.000000 C -2.079158 -1.446328 0.000000 C -0.723645 -1.862769 0.000000 C -1.372789 0.920102 0.000000 H -0.484523 -2.909151 0.000000 H 3.745534 -0.698218 0.000000 H 1.925488 -2.357604 0.000000 H 0.861899 2.465004 0.000000 H 3.213080 1.722144 0.000000 H -3.439948 0.201815 0.000000 H -2.853740 -2.191148 0.000000 ------------------------------------------ Triplet 1-naphthylnitrene CASSCF(12,12)/6-31G* -437.298816 CASPT2(12,12)/6-31G* -438.563904 reference weight 0.7006 ZPE 90.93 N -1.699259 2.168231 0.000000 C 2.710012 -0.377864 0.000000 C 1.695577 -1.309403 0.000000 C 0.334561 -0.903269 0.000000 C 0.034217 0.477636 0.000000 C 1.089433 1.420981 0.000000 C 2.403843 1.001486 0.000000 C -2.385004 -0.098283 0.000000 C -2.054773 -1.457573 0.000000 C -0.729745 -1.862322 0.000000 C -1.365686 0.892724 0.000000 H -0.484797 -2.908508 0.000000 H 3.735862 -0.697803 0.000000 H 1.924671 -2.359975 0.000000 H 0.857783 2.469154 0.000000 H 3.197768 1.725412 0.000000 H -3.409717 0.221279 0.000000 H -2.839287 -2.191532 0.000000 ------------------------------------------- TS connecting 1 and azirine 15 CASSCF(12,12)/6-31G* -437.268467 CASPT2(12,12)/6-31G* -438.532433 reference weight 0.7016 ZPE 90.57 N -1.941795 -1.732613 0.710190 C 2.723287 0.464567 -0.020062 C 1.632207 1.329840 0.073002 C 0.324037 0.833454 0.041867 C 0.136864 -0.562743 -0.081293 C 1.224535 -1.426354 -0.162098 C 2.522968 -0.910997 -0.136174 C -2.326959 -0.062591 -0.469015 C -2.118617 1.309130 -0.094170 C -0.839972 1.729379 0.142414 C -1.275918 -0.978662 -0.046698 H -0.646802 2.763840 0.361399 H 3.721613 0.861421 0.001968 H 1.796154 2.388567 0.165388 H 1.060725 -2.485156 -0.242692 H 3.364884 -1.575481 -0.197596 H -3.226868 -0.430469 -0.911156 H -2.932345 2.011245 -0.088294 -------------------------------------------- Azirine 15 CASSCF(12,12)/6-31G* -437.276796 CASPT2(12,12)/6-31G* -438.543990 reference weight 0.7028 ZPE 91.92 N 1.736799 1.382912 1.381517 C -1.881279 -0.317674 -2.022686 C -1.830789 -0.731824 -0.691369 C -0.718475 -0.436442 0.105282 C 0.337493 0.303464 -0.477293 C 0.289197 0.723510 -1.802276 C -0.826248 0.407158 -2.579741 C 1.692565 -0.216084 1.679179 C 0.467829 -0.778980 2.288594 C -0.646033 -0.866165 1.521044 C 1.390046 0.547808 0.505802 H -1.541848 -1.297738 1.931540 H -2.740783 -0.557089 -2.621545 H -2.650290 -1.288757 -0.273636 H 1.103566 1.288101 -2.216797 H -0.874425 0.728286 -3.603768 H 2.651499 -0.669922 1.839908 H 0.468136 -1.161997 3.293295 --------------------------------------------- Azirine 11 (11 is a minimum at this level) CASSCF(12,12)/6-31G* -437.240539 CASPT2(12,12)/6-31G* -438.507015 reference weight 0.7013 ZPE 90.58 N 0.893318 -1.511247 1.109914 C -2.574892 0.631365 0.022072 C -1.500149 1.388984 0.350298 C -0.157520 0.839849 0.205884 C -0.041312 -0.613365 -0.011103 C -1.211798 -1.340458 -0.493299 C -2.423205 -0.739981 -0.461518 C 2.482927 -0.288409 -0.459292 C 2.257920 1.046223 -0.371415 C 0.976502 1.598121 0.072630 C 1.337817 -1.052143 0.027482 H 0.912917 2.665678 0.185157 H -3.565535 1.041817 0.093505 H -1.617562 2.409665 0.667437 H -1.094393 -2.363730 -0.797949 H -3.300651 -1.273003 -0.778319 H 3.389511 -0.728557 -0.823563 H 3.028625 1.740664 -0.652860 ---------------------------------------------- Singlet 2-naphthylnitrene. CASSCF(12,12)/6-31G* -437.2732321 CASPT2(12,12)/6-31G* -438.5339022 reference weight 0.7014 ZPE 90.45 N 3.466988 -0.356755 0.000000 C -2.856236 0.486629 0.000000 C -2.068374 -0.670332 0.000000 C -0.677354 -0.593054 0.000000 C -0.038916 0.694196 0.000000 C -0.864736 1.859859 0.000000 C -2.242639 1.753320 0.000000 C 0.158566 -1.790881 0.000000 C 1.355658 0.780525 0.000000 C 2.193144 -0.426660 0.000000 C 1.506345 -1.728566 0.000000 H -0.333870 -2.746746 0.000000 H -3.927197 0.406566 0.000000 H -2.541738 -1.636032 0.000000 H -0.395519 2.826933 0.000000 H -2.848873 2.640489 0.000000 H 1.848474 1.733621 0.000000 H 2.112358 -2.614388 0.000000 ---------------------------------------------- Triplet 2-naphthylnitrene CASSCF(12,12)/6-31G* -437.2978434 CASPT2(12,12)/6-31G* -438.5611335 reference weight 0.7011 ZPE 90.90 Charge=0 Multiplicity=3 N 3.487621 -0.339843 0.000000 C -2.853021 0.480164 0.000000 C -2.087099 -0.667832 0.000000 C -0.673733 -0.596658 0.000000 C -0.043777 0.677128 0.000000 C -0.856074 1.847611 0.000000 C -2.228581 1.751136 0.000000 C 0.145215 -1.780217 0.000000 C 1.371534 0.753416 0.000000 C 2.160670 -0.415084 0.000000 C 1.504450 -1.704598 0.000000 H -0.339376 -2.739960 0.000000 H -3.925340 0.412652 0.000000 H -2.561327 -1.633005 0.000000 H -0.379624 2.811458 0.000000 H -2.831332 2.640702 0.000000 H 1.859047 1.710586 0.000000 H 2.113016 -2.589177 0.000000 --------------------------------------------- TS connecting 2 and azirine 18 CASSCF(12,12)/6-31G* -437.2669356 CASPT2(12,12)/6-31G* -438.5291472 reference weight 0.7020 ZPE 90.48 N 2.826358 -1.020123 0.744577 C -2.774190 0.483189 0.188147 C -1.651951 1.313144 0.126585 C -0.374854 0.778137 -0.052851 C -0.226902 -0.632925 -0.170363 C -1.364350 -1.452411 -0.125736 C -2.630311 -0.899356 0.055869 C 0.804651 1.661126 -0.153664 C 1.101028 -1.124505 -0.466221 C 2.204004 -0.267612 -0.050823 C 2.070047 1.191230 -0.158225 H 0.623144 2.720757 -0.177950 H -3.749240 0.911249 0.331031 H -1.772205 2.378327 0.213401 H -1.249057 -2.516260 -0.228732 H -3.493715 -1.537505 0.097568 H 1.290512 -2.118947 -0.809877 H 2.929225 1.833940 -0.158674 --------------------------------------------- Azirine 18 CASSCF(12,12)/6-31G* -437.275645 CASPT2(12,12)/6-31G* -438.543044 reference weight 0.7028 ZPE 91.79 N 2.236861 -1.213456 0.796065 C -2.692560 0.580980 0.169671 C -1.542337 1.364080 0.119293 C -0.279570 0.780604 -0.058449 C -0.189063 -0.630935 -0.180008 C -1.353403 -1.402433 -0.149369 C -2.599753 -0.805329 0.030557 C 0.917066 1.651659 -0.142388 C 1.161967 -1.192978 -0.425538 C 2.199928 -0.282540 -0.050576 C 2.181200 1.173265 -0.145049 H 0.744838 2.712960 -0.162800 H -3.651045 1.046033 0.310567 H -1.621565 2.432472 0.215420 H -1.278224 -2.469459 -0.258380 H -3.486462 -1.411458 0.064665 H 1.307563 -1.959626 -1.162412 H 3.058822 1.787993 -0.163110 ---------------------------------------------- TS connecting nitrene 2 and azirine 14 CASSCF(12,12)/6-31G* -437.2403924 CASPT2(12,12)/6-31G* -438.5032816 reference weight 0.7012 ZPE 89.90 N -3.051514 -0.392974 0.768662 C 2.726961 0.691246 0.181288 C 1.571244 1.403105 0.156627 C 0.284258 0.760900 -0.025082 C 0.260692 -0.714289 -0.130724 C 1.538355 -1.415423 -0.131712 C 2.709054 -0.751867 0.025431 C -0.870633 1.507779 -0.188483 C -0.924549 -1.397511 -0.167977 C -2.117876 -0.562885 -0.059829 C -2.095444 0.829124 -0.470890 H -0.810757 2.580893 -0.224207 H 3.669508 1.191013 0.307038 H 1.589221 2.473374 0.255924 H 1.524772 -2.484962 -0.238332 H 3.639245 -1.289361 0.036640 H -0.973706 -2.468384 -0.216269 H -2.937051 1.288001 -0.940242 ---------------------------------------------- Azirine 14 CASSCF(12,12)/6-31G* -437.246691 CASPT2(12,12)/6-31G* -438.511937 reference weight 0.7028 ZPE 91.13 N 2.847222 0.165671 0.779482 C -2.664627 -0.795180 0.157945 C -1.476622 -1.442655 0.122746 C -0.212739 -0.732293 -0.046419 C -0.274489 0.752186 -0.115365 C -1.590860 1.380586 -0.104562 C -2.723366 0.652371 0.031634 C 0.960367 -1.427249 -0.210042 C 0.866414 1.507569 -0.137621 C 2.062439 0.693418 -0.051943 C 2.202524 -0.681481 -0.448249 H 0.938678 -2.501782 -0.258901 H -3.580216 -1.345480 0.272163 H -1.438296 -2.513870 0.203332 H -1.635118 2.451429 -0.188311 H -3.681097 1.139024 0.049373 H 0.867952 2.578986 -0.177097 H 2.913686 -1.006100 -1.183164 ----------------------------------------------- Singlet 1-naphthylnitrene. UB3LYP/6-31G* optimized geometry. UB3LYP/6-31G* -439.946557 S2 1.04 ZPE 86.90 UB3LYP/6-311+G(2d,p) -440.066610 S2 1.03 N -1.819723 2.111920 0.000000 C 2.708629 -0.232245 0.000000 C 1.731651 -1.211961 0.000000 C 0.357955 -0.868359 0.000000 C 0.000000 0.509921 0.000000 C 1.004255 1.489527 0.000000 C 2.344500 1.125849 0.000000 C -2.411929 -0.191159 0.000000 C -2.013940 -1.518051 0.000000 C -0.662725 -1.868593 0.000000 C -1.434813 0.880092 0.000000 H -0.369338 -2.914670 0.000000 H 3.758520 -0.511933 0.000000 H 2.008127 -2.263562 0.000000 H 0.716161 2.536299 0.000000 H 3.113093 1.893523 0.000000 H -3.460342 0.085868 0.000000 H -2.769661 -2.299092 0.00000 ============================= B. (U)B3LYP/6-31G* geometries ============================= Triplet 1-naphthylnitrene. UB3LYP/6-31G* - -439.956555 S2 2.06 ZPE 86.97 UB3LYP/6-311+G(2d,p) -440.076130 S2 2.06 N -1.797347 2.140255 0.000000 C 2.702607 -0.262889 0.000000 C 1.718449 -1.231926 0.000000 C 0.346535 -0.874995 0.000000 C 0.000000 0.508052 0.000000 C 1.018445 1.479763 0.000000 C 2.350990 1.101688 0.000000 C -2.404123 -0.157982 0.000000 C -2.024878 -1.498665 0.000000 C -0.683755 -1.862112 0.000000 C -1.421035 0.884977 0.000000 H -0.401409 -2.911506 0.000000 H 3.749994 -0.551825 0.000000 H 1.984362 -2.286283 0.000000 H 0.742573 2.529772 0.000000 H 3.128240 1.860661 0.000000 H -3.449978 0.130409 0.000000 H -2.791754 -2.268477 0.000000 ------------------------------------------------ TS connecting nitrene 1 and azirine 15 UB3LYP geometry. UB3LYP/6-31G* -439.919794 S2 0.24 ZPE 86.43 UB3LYP/6-311+G(2d,p) -440.042106 S2 0.21 N -2.007180 -1.767992 0.637898 C 2.702837 0.478607 0.030257 C 1.602462 1.326552 0.118535 C 0.293059 0.815598 0.063992 C 0.129624 -0.590383 -0.080920 C 1.234085 -1.435590 -0.167547 C 2.522552 -0.901985 -0.109950 C -2.353598 -0.116486 -0.444106 C -2.148348 1.249326 -0.092883 C -0.869030 1.686867 0.148118 C -1.274785 -1.022691 -0.070983 H -0.685777 2.740130 0.346443 H 3.706613 0.891993 0.074258 H 1.748882 2.399057 0.221869 H 1.082774 -2.506429 -0.268846 H 3.384480 -1.561102 -0.161320 H -3.248536 -0.486201 -0.920438 H -2.971333 1.959604 -0.124317 ---------------------------------------------- Azirine 15 B3LYP/6-31G* -439.934964 ZPE 87.70 B3LYP/6-311+G(2d,p) -440.054776 C 2.698815 0.552141 0.034338 C 1.553934 1.339854 0.117009 C 0.274045 0.762670 0.059095 C 0.198860 -0.656781 -0.059110 C 1.345485 -1.445373 -0.147773 C 2.598937 -0.837601 -0.101875 H -0.789215 2.646033 0.291324 H 3.677861 1.021464 0.075093 H 1.642782 2.419270 0.214243 C -0.940470 1.585069 0.103429 C -1.188483 -1.068102 -0.035390 H 1.253171 -2.523447 -0.237984 H 3.497325 -1.445529 -0.156499 C -2.371207 -0.311489 -0.438222 C -2.191303 1.121556 -0.156196 H -3.023034 1.818293 -0.240386 N -2.157983 -1.363911 0.720712 H -3.024692 -0.640371 -1.242612 ---------------------------------------------- TS connecting azirine 15 and ketenimine 16 B3LYP/6-31G* -439.907044 ZPE 86.20 B3LYP/6-311+G(2d,p) -440.028984 C -2.692143 0.566886 -0.059499 C -1.571820 1.324483 -0.287236 C -0.263006 0.754040 -0.174180 C -0.210912 -0.691009 -0.012251 C -1.383507 -1.444107 0.294460 C -2.601725 -0.819028 0.274051 H 0.774234 2.613679 -0.088970 H -3.673518 1.030149 -0.119250 H -1.659520 2.386277 -0.504506 C 0.902328 1.534804 -0.050782 C 1.042450 -1.172706 -0.280251 H -1.296439 -2.510404 0.479760 H -3.508111 -1.383061 0.472090 C 2.608170 -0.257062 0.358433 C 2.141934 1.043498 0.411054 H 2.769401 1.740543 0.967562 N 2.201761 -1.180854 -0.728180 H 3.351017 -0.650003 1.047777 ---------------------------------------------- Ketenimine 16 B3LYP/6-31G* -439.909759 ZPE 86.75 B3LYP/6-311+G(2d,p) -440.032823 C -2.694440 0.589515 -0.093949 C -1.576774 1.329872 -0.351815 C -0.269096 0.749366 -0.167141 C -0.228630 -0.715121 -0.013658 C -1.417652 -1.434197 0.347732 C -2.617931 -0.787778 0.320608 H 0.778412 2.578080 -0.008608 H -3.675439 1.047363 -0.193149 H -1.656703 2.375475 -0.639009 C 0.883229 1.495543 0.027664 C 0.970572 -1.234783 -0.366866 H -1.346939 -2.495201 0.569739 H -3.533411 -1.320083 0.560226 C 2.742101 -0.214109 0.268774 C 2.163334 1.003581 0.468127 H 2.772134 1.716163 1.023670 N 2.178866 -1.156078 -0.669069 H 3.681606 -0.500591 0.733759 --------------------------------------------- TS connecting ketenimine 16 and ylide 17 B3LYP/6-31G* -439.895869 ZPE 86.13 B3LYP/6-311+G(2d,p) -440.018224 C -2.683512 0.684817 0.160298 C -1.482449 1.374030 0.245606 C -0.241031 0.716129 0.058565 C -0.284788 -0.726767 -0.077135 C -1.519341 -1.382491 -0.241182 C -2.717682 -0.691169 -0.125540 H 0.784363 2.551746 -0.268676 H -3.615982 1.225791 0.302101 H -1.486036 2.441254 0.452566 C 0.944964 1.481044 -0.163266 C 0.905425 -1.516876 -0.011906 H -1.499951 -2.456658 -0.399508 H -3.666842 -1.206897 -0.231229 C 2.819927 -0.187013 0.055147 C 2.265546 1.052187 -0.289654 H 2.993392 1.828196 -0.523156 N 2.079088 -1.275210 0.403740 H 3.895085 -0.280313 0.176138 --------------------------------------------- Ylide 17 B3LYP/6-31G* -439.915223 ZPE 87.12 B3LYP/6-311+G(2d,p) -440.038921 C -2.586517 0.822018 0.229395 C -1.334651 1.408871 0.049901 C -0.171550 0.641401 -0.140735 C -0.333494 -0.779626 -0.200772 C -1.596022 -1.358427 -0.062248 C -2.718910 -0.566006 0.175974 H 0.946575 2.400250 -0.714735 H -3.457537 1.449857 0.394595 H -1.243472 2.491933 0.089190 C 1.094783 1.388106 -0.340666 C 0.882813 -1.548348 -0.562779 H -1.686838 -2.436467 -0.154505 H -3.695859 -1.028432 0.286428 C 2.654851 -0.287276 0.521609 C 2.366777 1.028470 -0.034163 H 3.171856 1.751038 -0.155628 N 1.858186 -1.236942 0.165608 H 3.409503 -0.464682 1.282302 ---------------------------------------------- Azirine 11 (11 is a transition state at this level) B3LYP/6-31G* -439.896131 ZPE 86.21 B3LYP/6-311+G(2d,p) -440.018271 N 1.006347 -1.951640 0.886052 C -2.574519 0.636273 0.038817 C -1.478852 1.409725 0.308548 C -0.157641 0.862792 0.190830 C -0.041458 -0.563775 -0.070801 C -1.199633 -1.324778 -0.385240 C -2.434132 -0.729943 -0.358317 C 2.472402 -0.261017 -0.363470 C 2.250591 1.088847 -0.283554 C 0.997933 1.640637 0.108398 C 1.354219 -1.087217 0.039608 H 0.913008 2.718859 0.213548 H -3.570501 1.064639 0.113293 H -1.586842 2.454690 0.588656 H -1.077125 -2.378316 -0.610305 H -3.318232 -1.306168 -0.613699 H 3.401936 -0.694332 -0.715988 H 3.059872 1.772839 -0.526777 ---------------------------------------------- Ketenimine 10 B3LYP/6-31G* -439.942525 ZPE 87.35 B3LYP/6-311+G(2d,p) -440.065761 C 2.549783 0.861331 0.219705 C 1.294715 1.432582 0.039004 C 0.135096 0.652643 -0.146825 C 0.318425 -0.761159 -0.185912 C 1.580281 -1.335327 -0.024918 C 2.694534 -0.528920 0.188620 H -1.021910 2.370093 -0.768244 H 3.416491 1.498109 0.372406 H 1.191509 2.514811 0.061406 C -1.142445 1.373615 -0.345334 C -1.810169 -1.204153 0.105167 H 1.668854 -2.415276 -0.088807 H 3.675390 -0.980955 0.306573 C -2.664493 -0.322346 0.594494 C -2.403193 0.990024 -0.020679 H -3.230698 1.673772 -0.208877 N -0.809628 -1.588709 -0.518929 H -3.347448 -0.489320 1.418117 ---------------------------------------------- Singlet 2-naphthylnitrene. (UB3LYP geometry) UB3LYP/6-31G* -439.942109 S2 1.04 ZPE 86.81 UB3LYP/6-311+G(2d,p) -440.062823 S2 1.04 C -2.812277 0.476120 0.000000 C -2.040453 -0.677127 0.000000 C -0.635979 -0.606878 0.000000 C 0.000000 0.682712 0.000000 C -0.818656 1.848077 0.000000 C -2.194333 1.745256 0.000000 H -0.304009 -2.755715 0.000000 H -3.896100 0.403446 0.000000 H -2.518548 -1.653804 0.000000 C 0.189367 -1.786280 0.000000 C 1.404108 0.762280 0.000000 H -0.338190 2.823148 0.000000 H -2.806563 2.642667 0.000000 C 2.222093 -0.419989 0.000000 C 1.544579 -1.717224 0.000000 H 1.899808 1.727952 0.000000 H 2.162830 -2.608464 0.000000 N 3.521440 -0.345846 0.000000 ---------------------------------------------- Triplet 2-naphthylnitrene. UB3LYP/6-31G* -439.953757 S2 2.06 ZPE 86.91 UB3LYP/6-311+G(2d,p) -440.073874 S2 2.06 C -2.811714 0.477717 0.000000 C -2.045771 -0.675095 0.000000 C -0.636832 -0.608338 0.000000 C 0.000000 0.679401 0.000000 C -0.814742 1.846105 0.000000 C -2.189671 1.746764 0.000000 H -0.307972 -2.755007 0.000000 H -3.895876 0.408986 0.000000 H -2.525544 -1.650967 0.000000 C 0.183517 -1.784737 0.000000 C 1.408126 0.754024 0.000000 H -0.331799 2.820052 0.000000 H -2.800000 2.645501 0.000000 C 2.210978 -0.420504 0.000000 C 1.543152 -1.711886 0.000000 H 1.903881 1.720219 0.000000 H 2.160788 -2.603875 0.000000 N 3.530610 -0.343660 0.000000 ---------------------------------------------- TS connecting nitrene 2 and azirine 18 (UB3LYP geometry) UB3LYP/6-31G* -439.916782 S2 0.24 ZPE 86.41 UB3LYP/6-311+G(2d,p) -440.039231 S2 0.21 N 2.847221 -1.085491 0.680849 C -2.736742 0.478352 0.178222 C -1.618573 1.308365 0.131463 C -0.330742 0.777757 -0.025070 C -0.178400 -0.643726 -0.130354 C -1.324390 -1.462585 -0.106758 C -2.589481 -0.909307 0.049588 C 0.833610 1.655044 -0.133129 C 1.140254 -1.141412 -0.407629 C 2.244697 -0.261888 -0.069271 C 2.104058 1.191805 -0.160781 H 0.644694 2.726492 -0.147762 H -3.725149 0.910254 0.307135 H -1.740603 2.386042 0.212688 H -1.203355 -2.538462 -0.203558 H -3.463703 -1.553585 0.079782 H 1.321990 -2.132512 -0.795636 H 2.969840 1.845774 -0.176270 ---------------------------------------------- Azirine 18 B3LYP/6-31G* optimized geometry. B3LYP/6-31G* -439.933926 ZPE 87.57 B3LYP/6-311+G(2d,p) -440.053779 C -2.659701 0.572628 0.169921 C -1.507490 1.349871 0.149100 C -0.238701 0.764440 -0.017140 C -0.149437 -0.657706 -0.140784 C -1.324733 -1.416997 -0.160795 C -2.569565 -0.814248 0.003613 H 0.759488 2.702179 -0.162546 H -3.629308 1.043803 0.305023 H -1.581084 2.429935 0.255771 C 0.941060 1.629571 -0.135819 C 1.196874 -1.227340 -0.369529 H -1.251941 -2.494444 -0.286554 H -3.470131 -1.422417 0.010075 C 2.239931 -0.268203 -0.028125 C 2.216080 1.166418 -0.177125 H 3.093507 1.798697 -0.250968 N 2.268005 -1.237225 0.786288 H 1.337526 -1.987790 -1.134729 ---------------------------------------------- TS connecting azirine 18 and ketenimine 19 B3LYP/6-31G* -439.905362 ZPE 86.12 B3LYP/6-311+G(2d,p) -440.026853 C -2.621941 0.627728 0.197668 C -1.466705 1.346557 0.335398 C -0.176985 0.751943 0.122715 C -0.119959 -0.696672 -0.069592 C -1.358335 -1.374885 -0.333039 C -2.563807 -0.746124 -0.178915 H 0.736083 2.663333 -0.201358 H -3.586442 1.106598 0.340496 H -1.506341 2.409227 0.562463 C 0.917896 1.590153 -0.159737 C 1.053274 -1.458065 -0.053886 H -1.320998 -2.433559 -0.577842 H -3.486095 -1.301570 -0.326275 C 2.415936 -0.123251 0.041477 C 2.198837 1.103549 -0.498032 H 2.923921 1.644061 -1.094652 N 2.208914 -1.113461 0.776259 H 1.108204 -2.419460 -0.560991 ---------------------------------------------- Ketenimine 19 B3LYP/6-31G* -439.909745 ZPE 86.75 B3LYP/6-311+G(2d,p) -440.032359 C -2.589223 0.697037 -0.191638 C -1.417390 1.371270 -0.345733 C -0.134307 0.754430 -0.083945 C -0.132307 -0.718150 0.113619 C -1.413189 -1.351107 0.361307 C -2.587246 -0.683098 0.205805 H 0.833558 2.649172 -0.102560 H -3.536477 1.206114 -0.346088 H -1.422845 2.427915 -0.601085 C 0.963194 1.582411 0.085598 C 0.940634 -1.565108 -0.096659 H -1.412661 -2.408632 0.613259 H -3.532316 -1.195823 0.361093 C 2.500126 -0.094605 -0.037762 C 2.240957 1.072330 0.545200 H 2.879800 1.567702 1.267610 N 2.163287 -1.142981 -0.652983 H 0.820432 -2.638040 0.043897 ---------------------------------------------- TS connecting ketenimine 19 and ylide 20 B3LYP/6-31G* -439.889867 ZPE 86.32 B3LYP/6-311+G(2d,p) -440.011983 C 2.620021 0.741523 -0.131380 C 1.415420 1.410213 -0.154969 C 0.166768 0.737843 -0.001824 C 0.221143 -0.703807 0.118132 C 1.481993 -1.356125 0.146752 C 2.666129 -0.660479 0.033676 H -0.845337 2.613235 -0.002008 H 3.545460 1.301303 -0.239289 H 1.401207 2.490541 -0.272020 C -1.000476 1.540201 0.116943 C -0.929999 -1.555474 0.113127 H 1.494902 -2.438256 0.253461 H 3.619069 -1.179053 0.068348 C -2.735017 -0.083133 -0.316321 C -2.315633 1.084771 0.315402 H -3.071397 1.776433 0.684391 N -2.132841 -1.270139 -0.327029 H -0.756118 -2.606426 0.359098 ---------------------------------------------- Ylide 20 B3LYP/6-31G* -439.915293 ZPE 87.24 B3LYP/6-311+G(2d,p) -440.038541 C -2.575162 0.835061 0.149567 C -1.321385 1.425910 0.003762 C -0.148426 0.661905 -0.129528 C -0.285397 -0.759018 -0.120913 C -1.550862 -1.341222 0.015500 C -2.693947 -0.555320 0.151211 H 0.957449 2.449873 -0.613330 H -3.457771 1.460398 0.250767 H -1.240747 2.510315 -0.011799 C 1.116416 1.412352 -0.319450 C 0.910935 -1.581288 -0.355084 H -1.632460 -2.425271 -0.000894 H -3.669377 -1.024047 0.245924 C 2.607817 -0.200314 0.699346 C 2.394151 1.065913 -0.006837 H 3.194322 1.796114 -0.094732 N 2.035208 -1.151484 0.092600 H 0.877296 -2.490869 -0.949593 ---------------------------------------------- TS connecting nitrene and azirine 14 (UB3LYP geometry) UB3LYP/6-31G* -439.895540 S2 0.28 ZPE 85.58 UB3LYP/6-311+G(2d,p) -440.017338 S2 0.25 N -3.122079 -0.353528 0.721758 C 2.696000 0.673446 0.182399 C 1.525720 1.385407 0.159818 C 0.261238 0.739891 0.002655 C 0.238681 -0.721655 -0.120294 C 1.497882 -1.417472 -0.125943 C 2.678139 -0.747840 0.033810 C -0.920329 1.484145 -0.173927 C -0.964416 -1.413038 -0.172488 C -2.142079 -0.604896 -0.036520 C -2.136877 0.830436 -0.405223 H -0.844746 2.561040 -0.313725 H 3.646126 1.186389 0.300364 H 1.539462 2.468739 0.251434 H 1.484729 -2.499179 -0.231622 H 3.616354 -1.295845 0.043710 H -1.009187 -2.491985 -0.279502 H -2.981946 1.294995 -0.888690 ----------------------------------------------- Azirine 14 B3LYP/6-31G* -439.907974 ZPE 86.34 B3LYP/6-311+G(2d,p) -440.027861 C -2.621294 -0.781203 0.166254 C -1.415794 -1.421926 0.127333 C -0.178859 -0.703944 -0.008743 C -0.243955 0.758615 -0.102288 C -1.539398 1.378691 -0.093444 C -2.680934 0.641503 0.048275 H 0.942403 -2.429604 -0.598185 H -3.541132 -1.348838 0.273651 H -1.367778 -2.505935 0.196392 C 1.016187 -1.396191 -0.261085 C 0.918380 1.531035 -0.208810 H -1.588498 2.461350 -0.176419 H -3.647460 1.138051 0.065228 C 2.066204 0.772743 0.040451 C 2.266573 -0.731255 -0.355401 H 0.918939 2.585361 -0.458724 N 2.819751 0.123204 0.807326 H 3.022610 -1.051223 -1.068463 ----------------------------------------------- TS connecting azirine 14 and keteimine 13 B3LYP/6-31G* -439.907972 ZPE 86.15 B3LYP/6-311+G(2d,p) -440.027901 C -2.620375 -0.782510 0.167176 C -1.413279 -1.421783 0.126903 C -0.178390 -0.702306 -0.008564 C -0.244909 0.758253 -0.102141 C -1.539671 1.377227 -0.092570 C -2.681394 0.638962 0.049620 H 0.942540 -2.421395 -0.620908 H -3.539221 -1.351643 0.275239 H -1.364104 -2.505795 0.195412 C 1.018603 -1.393909 -0.266539 C 0.918519 1.532532 -0.214770 H -1.589863 2.459845 -0.175526 H -3.648110 1.135160 0.067116 C 2.063867 0.780970 0.046855 C 2.270051 -0.737250 -0.349338 H 0.919219 2.582327 -0.482728 N 2.812994 0.122548 0.808466 H 3.030456 -1.057453 -1.057658 ----------------------------------------------- Ketenimine 13 B3LYP/6-31G* -439.941309 ZPE 87.50 B3LYP/6-311+G(2d,p) -440.064211 C -2.562281 -0.871213 -0.165797 C -1.301389 -1.432105 0.003429 C -0.146725 -0.638749 0.156745 C -0.311587 0.781025 0.150085 C -1.588514 1.331649 -0.031436 C -2.708363 0.519024 -0.179685 H 1.021796 -2.374073 0.726841 H -3.430178 -1.514603 -0.280266 H -1.194782 -2.514305 0.016706 C 1.131746 -1.359390 0.348068 C 0.873787 1.632478 0.415880 H -1.694764 2.413281 -0.029932 H -3.692152 0.965915 -0.294653 C 1.953840 1.125931 -0.146548 C 2.390342 -0.994927 0.006675 H 0.855806 2.487834 1.080361 N 2.644466 0.233709 -0.671164 H 3.237874 -1.662342 0.134590 ----------------------------------------------- Nitrile ylide 30 B3LYP/6-31G* -286.2557386 ZPE 57.34 6 1.634300 -0.056953 0.132148 1 2.692096 -0.097531 0.382169 1 1.528573 2.000041 0.493104 6 0.949450 1.117094 0.224586 6 -0.439106 1.397262 -0.164540 6 -1.494048 0.542707 -0.137744 6 -1.291464 -0.834616 0.303150 1 -0.633173 2.428279 -0.456905 1 -2.489296 0.891338 -0.408423 1 -2.007252 -1.374908 0.917540 7 -0.157931 -1.375263 0.016464 6 0.976629 -1.202224 -0.531389 -------------------------------------------------- Ketenimine 31 B3LYP/6-31G* -286.28471 ZPE 57.62 6 0.004039 -1.315619 -0.032056 7 -1.146099 -1.082220 -0.462775 6 -1.588203 0.129918 0.148252 6 -0.770171 1.212266 0.231439 6 0.630508 1.315866 -0.174403 6 1.573893 0.333539 -0.149241 6 1.234625 -1.008527 0.347530 1 -2.633886 0.171530 0.442820 1 -1.237975 2.139908 0.556566 1 0.944021 2.305745 -0.503217 1 2.584520 0.551629 -0.495133 1 1.857866 -1.597930 1.009258 ------------------------------------------------- Planar keteimine 31' constrained in Cs symmetry B3LYP/6-31G* -286.2413897 ZPE 56.14 1 imaginary freq. at -730 cm-1 7 -1.171397 1.063329 0.000000 6 0.000000 1.342198 0.000000 6 1.322364 1.199560 0.000000 6 1.559047 -0.277685 0.000000 6 0.682221 -1.308264 0.000000 6 -0.822491 -1.316252 0.000000 6 -1.674892 -0.285506 0.000000 1 2.096214 1.947266 0.000000 1 2.617376 -0.535776 0.000000 1 1.117950 -2.302709 0.000000 1 -1.276742 -2.303888 0.000000 1 -2.752513 -0.372497 0.000000 --------------------------------------------------- Planar iminocarbene, constrained to Cs symmetry B3LYP/6-31G* -286.2200447 ZPE 56.46 2 imaginary freq. at -1024 & -506 cm-1 6 -1.756187 -0.198393 0.000000 7 -1.246351 1.102333 0.000000 6 0.000000 1.537697 0.000000 6 1.267165 0.890082 0.000000 6 1.514408 -0.463271 0.000000 6 0.542099 -1.486763 0.000000 6 -0.834293 -1.334627 0.000000 1 0.076463 2.631314 0.000000 1 2.128968 1.555678 0.000000 1 2.556729 -0.777685 0.000000 1 0.932460 -2.506092 0.000000 1 -1.369319 -2.287899 0.000000 --------------------------------------------------- ================================================== C. Lists of observed and calculated IR frequencies ================================================== (All frequencies calculated by B3LYP/6-31G* and scaled by 0.97) ************** * 1-NaN3 * ************** ------------------------------------------------ triplet 1-NaN (3-1) 24.spc anaz7dc.spc calc.(scaled) expt. 1609 1608 1492 1492 1312 1312d 1275 1278 1223 1229d 1206 1213 1138 1139 1081 1090 1015 1019 780 786 757 760 713 713 ------------------------------------------------ azirine 15 25.spc anaz7gf.spc calc.(scaled) expt. 1760 1730 1459 1465 1452 1456 923m 932m 874 885 810 806 769 775 745 752 718 727 583 585 521 523 ------------------------------------------------ ylide 17 (26-prime.spc anaz7lk.spc) calc.(scaled) expt. 1708 1683 1595 1592 1583 1577 1559 1555 1458 1462 1417 1414 1384 1381 1224 1227 1210 1211 1071 1086 833 842 811 822 764 764 (buried under other bands) 771 773 747 753 712 717 704 710 ------------------------------------------------ quinoid structure 16 the biggest calculated IR signal at 1827 cm-1 is not observed in the experiments ------------------------------------------------ ketenimine 10 calc.(scaled) expt. 1945 1912-1930 ------------------------------------------------ ************** * 2-NaN3 * ************** ------------------------------------------------ triplet 2-NaN (3-2) 29.spc bnaz4cb.spc/4dc.spc calc.(scaled) expt. 1604 1597b 1587 1377 1381 1290 1299 1183 1185 1108 1112 825 836 (coincides with a band of 20) 797 802 737 745 610 611 ------------------------------------------------ azirine 18 30.spc bnaz4cb.spc calc.(scaled) expt. 1755 1733, 1723, 1707 1610 1604 1543 1538 1446 1446 1194 1196 1168 1170 1156 1157 979 978 905 913 866 874 854 855 772 780 743 752 678 685 652 641 596 596 569 574 538 538 ------------------------------------------------ ylide 20 31-prime.spc bnaz4cb.spc/4dc.spc calc.(scaled) expt. 1707 0 1697, 1680, 1668 1478 1481 1392 1389 1262 1264 1219 1208d 1132 1135 963 963 941 945d 879 886 838 836 751 758 612 620 ------------------------------------------------ quinoid structure 19 the most intense calculated IR signal at 1849 cm-1 is not observed in the experiments ------------------------------------------------ ketenimine 13 33.spc bnaz5dc.spc calc.(scaled) expt. 1940 1913 1601 1596 1471 1476 1442 1440 1373 1367 1248 1248 1214 1216 1117 1116 1093 1096 966 963 876 885 824 826 764 768 749 756 668 671 613 623 517 520 ------------------------------------------------