Table I-A. Ab initio calcuations of absolute gas-phase electronic energy, including nuclear repulsion (in hartrees) for 1a-4a.a
level of theory 1a 2a 3a 4a HF/3-21Gb,c -317.66429 -317.66602 -317.65941 -317.65387HF/DB1b -319.48533 -319.49314 -319.48301 -319.47997
HF/DB2 -319.50227 -319.50865 -319.49824 -319.49529
HF/DB3 -319.570911 -319.576148 -319.56699 -319.56388
HF/DB3b -319.578959 -319.585395 ... ...
HF/DB4 -319.57546 -319.58043 -319.57122 -319.56816
HF/DB3//HF/DB1 -319.578621 -319.585125 ... ...
MP2/DB1 -320.39293 -320.40305 -320.39747 -320.39536
MP2/DB2 -320.461197 -320.469252 -320.46438 -320.46235
MP2/DB2b -320.461403 -320.469466 ... ...
MP2/DB3 -320.70429 -320.71064 -320.70863 -320.70647
MP2/DB4 -320.730075 -320.73573 -320.73367 -320.73153
MP3/DB1 -320.40289 -320.41426 -320.40707 -320.40481
MP3/DB2 -320.46903 -320.47871 -320.47129 -320.46915
MP4/DB1 -320.45896 -320.47163 -320.46055 -320.45828
MP4/DB2 -320.53231 -320.54280 -320.53240 -320.53020
CCSD/DB1 -320.41653 -320.42915 -320.41826 -320.415781
CCSD/DB1d -320.41655 ... ... ...
CCSD(T)/DB1 -320.45329 -320.46582 -320.45521 -320.452708
CCSD/DB2 -320.48136 -320.49224 -320.48140 -320.48116
a All geometries are from MP2/DB1 optimizations unless otherwise indicated. bGeometry optimized at same level. cValue for planar TS of 1a is -317.66189 in agreement with value reported by Woodcock et al. in
Woodcock, S.; Green, D. V. S.; Vincent, M. A.; Hillier, I. H.; Guest, M. F.; Sherwood, P. J. J. Chem. Soc., Perkin Trans. 2 1992, 2151.
dCoordinates of NH proton optimized at this level.
Table II-A. AM1 gas-phase heats of formation (in kcal/mol).
substitution pattern 1 2 3 4
a -4.83 -14.62 -1.91 0.42
b -13.91 -22.65 -9.82 -7.46
c -13.30 -19.62 -9.78 -7.78
d -22.02 -27.25 -17.15 -15.14
Table III-A. SCRF/6-31G** Onsager-reaction-field calculations.a,b
rcavity (Å) 1ac 2a 3a 4a
2.5 -319.50708c -319.50308 -319.46049 -319.48164
(0.0) (2.5) (29.2) (16.0)
3.60-3.62d -319.46824 -319.47542 -319.45687 -319.45901
(4.5) (0.0) (11.6) (10.3)
aAbsolute
energies in hartrees and relative free energies in aqueous solution (in
parentheses in kcal/mol). bHF/3-21G geometries are used. cValues for planar TS of 1a are - 319.51156 (-2.8) in agreement with those reported by Woodcock et al. Using rcavity = 3.6 Å gives - 319.46317 (7.7). dCalculated using the WWF isodensity surface; see reference 4g and text. Gas phase Z-matrices and energies (Gaussian 92 archive format) at MP2/cc-pVDZ geometries for 1a-4a:
1a:
1\1\GINC-SF\SP\RCCSD(T)\Gen\C3H3N1O2\MG37501\4-Feb-1993\0\\# CCSD(T) G EN SCF=DIRECT\\isomer one, coupled cluster DZ\\0,1\O\C,1,1.41137425\N ,1,1.41166775,2,108.29420861\C,2,1.46618701,1,105.99356153,3,-5.034803 22,0\C,3,1.39116011,1,107.06085954,2,8.72555717,0\O,2,1.20841149,1,120 .74477086,3,174.59262445,0\H,5,1.09188658,3,118.44892511,1,174.7433116 2,0\H,4,1.08730908,2,124.51571873,1,179.74692221,0\H,3,1.02490315,1,10 6.9918742,2,133.42126915,0\\Version=CrayYMP-Unicos-G92RevB\HF=-319.479 4011\MP2=-320.3929301\MP3=-320.402885\MP4D=-320.4248554\MP4DQ=-320.404 8054\MP4SDQ=-320.4185976\CCSD=-320.4165342\CCSD(T)=-320.4532939\RMSD=3 .683e-09\PG=C01 [X(C3H3N1O2)]\\@
2a:
1\1\GINC-SI\SP\RCCSD(T)\Gen\C3H3N1O2\MG37501\3-Feb-1993\0\\# CCSD(T) G EN SCF=DIRECT\\isomer two, coupled cluster DZ\\0,1\O\C,1,1.39088493\N ,1,1.41870517,2,110.45663044\C,2,1.52355657,1,107.11424305,3,0.,0\C,3, 1.29831228,1,108.30466611,2,0.,0\O,2,1.20292901,1,122.26764856,3,180., 0\H,5,1.09251224,3,117.96929005,1,180.,0\H,4,1.10250403,2,110.41907526 ,1,120.35423828,0\H,4,1.10250403,2,110.41907526,1,-120.35423828,0\\Ver sion=CrayYMP-Unicos-G92RevB\State=1-A'\HF=-319.4859361\MP2=-320.403045 4\MP3=-320.4142584\MP4D=-320.4379452\MP4DQ=-320.4179123\MP4SDQ=-320.43 16473\CCSD=-320.429146\CCSD(T)=-320.4658246\RMSD=8.637e-09\PG=CS [SG(C 3H1N1O2),X(H2)]\\@
3a:
1\1\GINC-SI\SP\RCCSD(T)\Gen\C3H3N1O2\MG37501\13-Feb-1993\0\\# CCSD(T) GEN SCF=DIRECT\\isomer three, coupled cluster DZ\\0,1\O\C,1,1.34653877 \N,1,1.39999874,2,109.09779225\C,2,1.37344802,1,111.04174953,3,0.,0\C, 3,1.32922938,1,104.66142617,2,0.,0\O,2,1.34177987,1,117.39488018,3,180 .,0\H,5,1.09083869,3,118.05665089,1,180.,0\H,4,1.08597164,2,127.920755 61,1,180.,0\H,6,0.97119467,2,106.71323307,1,0.,0\\Version=CrayYMP-UniC os-G92RevB\State=1-A'\HF=-319.4766162\MP2=-320.3974735\MP3=-320.407073 \MP4D=-320.4290546\MP4DQ=-320.4076048\MP4SDQ=-320.4195463\CCSD=-320.41 82627\CCSD(T)=-320.4552091\RMSD=8.444e-09\PG=CS [SG(C3H3N1O2)]\\@
4a:
1\1\GINC-SI\SP\RCCSD(T)\Gen\C3H3N1O2\MG37501\13-Feb-1993\0\\# CCSD(T) GEN SCF=DIRECT\\isomer four, coupled cluster DZ\\0,1\O\C,1,1.3403601 5\N,1,1.39672594,2,109.01179173\C,2,1.37699754,1,111.1319008,3,0.,0\C, 3,1.32881548,1,105.09704491,2,0.,0\O,2,1.34485359,1,113.46381653,3,180 .,0\H,5,1.0907025,3,118.3394741,1,180.,0\H,4,1.08727575,2,128.57730004 ,1,180.,0\H,6,0.96876562,2,106.66986607,1,180.,0\\Version=CrayYMP-Unic os-G92RevB\State=1-A'\HF=-319.4731927\MP2=-320.3953646\MP3=-320.404808 7\MP4D=-320.4268825\MP4DQ=-320.4053631\MP4SDQ=-320.4171965\CCSD=-320.4 157811\CCSD(T)=-320.4527075\RMSD=9.806e-09\PG=CS [SG(C3H3N1O2)]\\@
Gas phase Z-matrices and energies (Gaussian 92 archive format) at MP2/acc-pVDZ geometries for 1a and 2a:
1a:
1\1\GINC-SF\FOPT\RMP2-FC\Gen\C3H3N1O2\MG37501\7-Mar-1993\1\\# MP2 GEN SCF=DIRECT OPT=(CALCHFFC,NOEIGENTEST,EXPERT,NORAMAN)\\isomer one, cou pled cluster DZ\\0,1\O\C,1,r1\N,1,r2,2,ba\C,2,r3,1,bb,3,d1,0\C,3,r4,1, bc,2,d2,0\O,2,r5,1,bd,3,d3,0\H,5,r6,3,be,1,d4,0\H,4,r7,2,bf,1,d5,0\H,3 ,r8,1,bg,2,d6,0\\r8=1.02302915\bg=107.06098774\d6=133.92987309\r1=1.42 150098\r2=1.4196197\r3=1.46170715\r4=1.39148665\r5=1.21504725\r6=1.090 48092\r7=1.08628316\ba=107.96823142\bb=106.06095543\bc=107.06639875\bd =120.39935616\be=118.41604778\bf=124.40374004\d1=-4.81054255\d2=8.1449 7503\d3=174.69525921\d4=174.87617873\d5=179.53801874\\Version=CrayYMP- Unicos-G92RevB\HF=-319.5004409\MP2=-320.461403\RMSD=4.765e-09\RMSF=5.5 99e-05\Dipole=1.8898503,-0.5796003,-0.6257554\PG=C01 [X(C3H3N1O2)]\\@
2a:
1\1\GINC-SJ\FOPT\RMP2-FC\Gen\C3H3N1O2\MG37501\8-Mar-1993\1\\# MP2 GEN SCF=DIRECT OPT=(CALCHFFC,NOEIGENTEST,EXPERT,NORAMAN)\\isomer two, MP2 opt DZ+\\0,1\O\C,1,r1\N,1,r2,2,ba\C,2,r3,1,bb,3,0.,0\C,3,r4,1,bc,2,0. ,0\O,2,r5,1,bd,3,180.,0\H,5,r6,3,be,1,180.,0\H,4,r7,2,bf,1,d1,0\H,4,r7 ,2,bf,1,-d1,0\\r1=1.39617043\r2=1.43466944\r3=1.52106173\r4=1.30034308 \r5=1.20921255\r6=1.09108358\r7=1.10093859\ba=110.13488557\bb=107.2326 7222\bc=108.05470917\bd=122.12108281\be=117.84195297\bf=110.25427003\d 1=120.28891036\\Version=CrayYMP-Unicos-G92RevB\State=1-A'\HF=-319.5066 844\MP2=-320.4694658\RMSD=7.456e-09\RMSF=2.266e-05\Dipole=1.6676864,0. ,0.7067249\PG=CS [SG(C3H1N1O2),X(H2)]\\@