#High-Spin Carbonyl Complexes of Iron(I) and Cobalt(I) #Christian Schneider, Lukas Guggolz, C. Gunnar Werncke #Philipps University Marburg, Germany #------.-------------------------------------------------------------------- #COMPUTATIONAL METHODS: #Turbomole V7.5.1 #dhf-TZVP + auxiliary basis sets + ECPs #B97-D3, BJ damping #COSMO for anionic molecules #Mulliken analyses, NPA, Paboon #--------------------------------------------------------------------------- #COORDINATES: #Optimized Structure of [Co(CO)(hmds)2]-, high-spin, He = -3243.4662853590 Co 1.2169833 -2.9393100 10.9614869 N 2.5444003 -3.1855086 12.3638203 N -0.7007527 -2.7976099 11.2593506 Si -1.2540726 -1.7366501 12.4897142 Si 2.1987680 -4.3869210 13.5453027 Si 4.0034606 -2.2863623 12.2525882 Si -1.6972785 -3.5695847 10.0960780 C 1.8924921 -2.6100875 9.3837761 C -2.5934129 -0.5326965 11.8789305 C 0.1353234 -0.6472072 13.1696223 C -2.0033152 -2.6710261 13.9640094 C 3.6531680 -5.5880359 13.7894141 C 1.7997001 -3.6533078 15.2511029 C 0.7310520 -5.4763231 13.0560611 C 3.7367557 -0.5409504 11.5653348 C 5.2751800 -3.1457827 11.1388153 C 4.8319062 -2.0046284 13.9422272 C -0.8938772 -5.1385613 9.3985264 C -2.0730632 -2.4396233 8.6193332 C -3.3605150 -4.1385220 10.8193474 O 2.3141992 -2.3519310 8.3127444 H 3.3535306 -0.5616176 10.5399105 H 4.6817796 0.0190464 11.5704461 H 3.0133293 0.0050098 12.1820821 H -2.2117863 0.0817830 11.0536441 H -2.9008539 0.1426168 12.6891253 H -3.4883692 -1.0536794 11.5195989 H 0.9907397 -1.2455713 13.4976732 H -0.2287273 -0.0507903 14.0176055 H 0.4967615 0.0440818 12.3983306 H 3.9005050 -6.0860638 12.8431961 H 3.3888948 -6.3637320 14.5208940 H 4.5577577 -5.0839861 14.1470746 H 2.6507769 -3.0883137 15.6487886 H 1.5534455 -4.4458920 15.9703851 H 0.9438619 -2.9717645 15.1923274 H 0.0528132 -4.9092804 8.8947565 H -1.5601320 -5.6240124 8.6721785 H -0.6811142 -5.8553632 10.2003127 H -2.8752991 -3.2603557 13.6566767 H -2.3235751 -1.9709465 14.7473395 H -1.2744625 -3.3610372 14.4037234 H -0.1605433 -4.8816866 12.8376951 H 0.5037841 -6.1786208 13.8699249 H 0.9633297 -6.0619816 12.1578862 H 5.5360851 -4.1333787 11.5386979 H 6.1983957 -2.5572202 11.0536100 H 4.8659562 -3.2873776 10.1309307 H -2.6143349 -1.5431084 8.9445507 H -2.6811384 -2.9507937 7.8609345 H -1.1382732 -2.1143325 8.1456956 H -3.1976711 -4.8398846 11.6468652 H -3.9523383 -4.6538882 10.0508954 H -3.9596854 -3.3042885 11.2010628 H 4.1691827 -1.4340629 14.6047745 H 5.7567846 -1.4257609 13.8150754 H 5.0913089 -2.9385968 14.4527354 #Optimized Structure of [Fe(CO)(hmds)2]-, high-spin, He = -3124.3137844340 Fe 1.2644855 -2.7589535 10.9529312 N 2.5269893 -3.1396963 12.4236037 N -0.6958457 -2.7240099 11.2500203 Si -1.2565145 -1.7346481 12.5349574 Si 2.2169209 -4.4016413 13.5381550 Si 3.9816558 -2.2455675 12.2849740 Si -1.6795200 -3.5106256 10.0857884 C 1.8533126 -2.8882021 9.2730243 C -2.5931794 -0.5039401 11.9746947 C 0.1396741 -0.6657603 13.2398747 C -1.9900850 -2.7249293 13.9783731 C 3.6995888 -5.5728252 13.7496398 C 1.7923503 -3.7515377 15.2712926 C 0.7764397 -5.4851072 12.9651702 C 3.6383689 -0.5497699 11.5031938 C 5.2710142 -3.1165676 11.2019249 C 4.7974963 -1.8777932 13.9605309 C -0.9328400 -5.1441052 9.4791609 C -1.9704255 -2.4244432 8.5586623 C -3.3893956 -3.9977033 10.7653675 O 2.3367670 -3.0657097 8.1998645 H 3.1293105 -0.6418407 10.5344753 H 4.5766597 -0.0041280 11.3344384 H 3.0052142 0.0579103 12.1600057 H -2.2112166 0.1324142 11.1660375 H -2.8890142 0.1491041 12.8070135 H -3.4942773 -1.0058827 11.6050956 H 0.9912388 -1.2708816 13.5672688 H -0.2266034 -0.0807421 14.0944931 H 0.5062898 0.0426870 12.4852336 H 3.9719213 -6.0246775 12.7873803 H 3.4547314 -6.3839786 14.4487913 H 4.5841971 -5.0535239 14.1363929 H 2.6322738 -3.1829426 15.6891692 H 1.5635273 -4.5745902 15.9615639 H 0.9233400 -3.0850403 15.2370135 H 0.0374350 -4.9873165 8.9954790 H -1.6055799 -5.6257261 8.7561880 H -0.7829639 -5.8354363 10.3168331 H -2.8729888 -3.2916404 13.6599613 H -2.2902773 -2.0588135 14.7983913 H -1.2605631 -3.4406257 14.3736752 H -0.1186295 -4.8879785 12.7666941 H 0.5409538 -6.2406175 13.7267244 H 1.0334137 -6.0089371 12.0358686 H 5.5498224 -4.0852660 11.6337825 H 6.1832297 -2.5145472 11.0946736 H 4.8595738 -3.2990800 10.2017442 H -2.4765129 -1.4919412 8.8386469 H -2.5861535 -2.9344200 7.8057173 H -1.0105827 -2.1615657 8.0968336 H -3.2830531 -4.6815777 11.6166096 H -3.9701535 -4.5146267 9.9894761 H -3.9749054 -3.1349969 11.1020292 H 4.1098158 -1.3210915 14.6091108 H 5.7002880 -1.2677639 13.8211310 H 5.0908013 -2.7918627 14.4898432 #Optimized Structure of [Fe(CO)(hmds)2]-, low-spin, He = -3124.3033417030 Fe 1.0684250 -2.9107018 11.3994051 N 2.5385829 -3.0693261 12.5782995 N -0.8220922 -2.8635014 11.3798965 C 1.6363055 -2.7578074 9.8537826 Si -1.4795166 -1.6797988 12.4477752 C -2.3642352 -0.2811949 11.5231293 C -0.1565020 -0.8682147 13.5332516 C -2.7244956 -2.4488696 13.6558645 Si 2.4119792 -4.4210761 13.6413041 C 3.7503277 -5.7251755 13.3176757 C 2.5491474 -3.8898793 15.4579856 C 0.7440280 -5.3052561 13.4922544 Si 3.9537960 -2.1412884 12.2639747 C 3.5463680 -0.3621653 11.7680888 C 5.0072357 -2.9076691 10.8884100 C 5.0781597 -2.0016661 13.7902158 Si -1.6501453 -3.6894635 10.1167115 C -0.8984916 -5.3885730 9.7615860 C -1.6405215 -2.6957096 8.5035810 C -3.4732972 -4.0125601 10.5450020 O 2.0444814 -2.6461518 8.7288040 H 2.9283647 -0.3445024 10.8642465 H 4.4640073 0.2135464 11.5833316 H 2.9846089 0.1373405 12.5669092 H -1.6706930 0.2160979 10.8336275 H -2.7528812 0.4722381 12.2211627 H -3.2068136 -0.6614373 10.9328955 H 0.4299865 -1.6041593 14.0940099 H -0.6498330 -0.1993193 14.2533232 H 0.5494957 -0.2806532 12.9377742 H 3.6812841 -6.0862621 12.2839656 H 3.6397947 -6.5861298 13.9903788 H 4.7566265 -5.3128249 13.4605579 H 3.5251297 -3.4494744 15.6863411 H 2.4028431 -4.7539440 16.1199179 H 1.7794321 -3.1455565 15.6970118 H 0.1576045 -5.2942227 9.4867479 H -1.4355169 -5.8944631 8.9473100 H -0.9560036 -6.0226715 10.6546072 H -3.5988692 -2.8623859 13.1435035 H -3.0753623 -1.6932513 14.3717319 H -2.2526094 -3.2599645 14.2243671 H -0.1019817 -4.6248840 13.6349629 H 0.6886882 -6.0929602 14.2573770 H 0.6222123 -5.7688241 12.5079598 H 5.2932102 -3.9332460 11.1523167 H 5.9265625 -2.3290404 10.7251147 H 4.4487198 -2.9431550 9.9470147 H -2.0919730 -1.7078478 8.6581320 H -2.2092974 -3.2108222 7.7177040 H -0.6149633 -2.5478334 8.1495678 H -3.5655888 -4.6230109 11.4511875 H -3.9580246 -4.5544558 9.7219438 H -4.0310708 -3.0824138 10.7060701 H 4.5577126 -1.5171454 14.6247712 H 5.9585999 -1.3932142 13.5430557 H 5.4348793 -2.9785789 14.1370929 #Optimized Structure of [Fe(CO)(hmds)2]- + cation, He = -4647.1259786960 Fe 1.6149614 5.1078425 14.0070196 N 0.6002992 4.9563351 12.3129208 N 2.0775300 3.4996854 15.0734271 C 1.5573382 6.6780136 14.8408025 K 3.8557770 8.8200214 16.3381859 O 4.7112486 6.7058776 17.9514251 O 5.7448072 6.8743103 15.2794226 O 3.4619528 8.9540293 19.1929028 O 2.0895340 10.7655805 17.4103110 O 3.0699408 11.0509420 14.6905707 O 4.4407147 8.7896369 13.6009330 O 1.3757445 7.7320765 15.3659696 Si 3.0570204 2.3630775 14.2407123 C 4.5476168 1.7892658 15.2693662 C 3.7496912 3.1238700 12.6480043 C 2.1485242 0.7769510 13.7257293 Si 0.9159464 6.2525464 11.2297408 C 2.7212222 6.8070874 11.3450537 C -0.1542556 7.7743444 11.5947539 C 0.6612924 5.7916435 9.4025949 Si -0.5974920 3.7555170 12.0603424 C -1.0715889 2.8710464 13.6624972 C -2.2315163 4.4783468 11.4069763 C -0.0435149 2.4407378 10.8058824 Si 1.5408363 3.3428136 16.6963090 C 2.8627581 3.7717329 17.9824101 C 0.0612811 4.4610234 17.0837895 C 0.9717316 1.5694330 17.0864828 C 5.7946100 5.9046143 17.4759630 C 4.7518739 6.9309678 19.3610579 C 5.5373408 6.6910708 13.8771962 C 5.6036298 5.6443810 16.0011899 C 2.2819725 9.6853571 19.5437191 C 3.4913530 7.6500924 19.7818574 C 2.0113243 11.9717686 16.6439772 C 2.2668072 11.0058349 18.8088666 C 1.8548547 11.6260041 15.1811269 C 2.9665674 10.6477175 13.3202823 C 5.5712652 8.0288524 13.1766456 C 4.2640318 10.0087506 12.8823510 H 3.7516858 3.1398925 17.8744020 H 2.4709586 3.6367558 18.9998297 H 3.1752942 4.8153816 17.8786350 H -0.1963637 2.4962536 14.1976296 H -1.7449457 2.0316489 13.4433167 H -1.5997579 3.5590617 14.3342440 H 2.9491640 7.2338863 12.3266991 H 2.9308366 7.5815022 10.5950683 H 3.4067325 5.9700572 11.1668579 H 4.5600446 6.2128855 13.7112496 H 6.3199272 6.0391273 13.4581483 H 5.1669982 2.6379041 15.5813947 H 5.1777860 1.1044010 14.6863149 H 4.2257339 1.2601534 16.1745534 H 5.8101993 4.9410940 18.0063140 H 6.7523151 6.4168802 17.6579942 H -1.2203385 7.5438683 11.4788133 H 0.0905016 8.6109350 10.9265786 H 0.0110845 8.1030367 12.6280733 H 2.9439633 3.4662509 11.9883685 H 4.3479988 2.3815362 12.1030170 H 4.4006115 3.9804289 12.8614468 H 6.5038598 8.5680844 13.4063237 H 5.5272830 7.8579686 12.0908467 H 6.3628718 4.9210835 15.6651766 H 4.6068563 5.2153669 15.8145127 H 2.9182882 12.5765340 16.7976339 H 1.1419124 12.5667526 16.9643152 H 5.6426724 7.5224403 19.6246958 H 4.8024192 5.9707598 19.8961490 H 0.3497222 5.5174171 17.0584011 H -0.3275149 4.2353331 18.0864132 H -0.7513647 4.3159710 16.3630702 H 1.4366534 11.6164653 19.1966457 H 3.2068801 11.5523793 18.9822707 H 2.2637645 9.8771411 20.6274816 H 1.3867220 9.0991963 19.2829584 H 1.7969524 0.2173746 14.5999216 H 2.8190594 0.1231923 13.1515889 H 1.2780403 1.0010711 13.1013803 H 0.1647761 1.2566391 16.4129026 H 0.5986165 1.5058761 18.1176345 H 1.7908604 0.8478998 16.9821149 H -2.6247219 5.2219815 12.1120644 H -2.9843353 3.6857814 11.2962817 H -2.1183055 4.9695450 10.4341418 H 1.0244806 10.9159929 15.0470865 H 1.6187606 12.5440491 14.6206922 H 0.0575067 2.8794852 9.8062991 H -0.7647534 1.6147226 10.7427443 H 0.9302791 2.0223575 11.0841355 H 2.6070818 7.0764914 19.4627298 H 3.4743413 7.7283304 20.8795940 H 1.3134555 4.9546741 9.1233244 H 0.9216732 6.6476984 8.7652809 H -0.3695393 5.5035307 9.1706156 H 2.7611097 11.5210038 12.6820277 H 2.1409436 9.9288836 13.2054467 H 4.2094227 9.8068904 11.8015321 H 5.1122778 10.6863546 13.0656583 #Optimized Structure of [Co(CO){N(SiH3)2}2]–, high-spin, He = -2771.6438460340 Co 1.2648774 -2.0769554 10.9902847 C 2.2160621 -1.1496323 9.8415181 O 2.8102208 -0.5503767 9.0278603 N -0.5952323 -2.5448543 11.2584298 N 2.4275514 -3.0593307 12.2091140 Si -1.1834534 -3.9248301 10.4353631 Si 4.1159239 -2.9486900 11.9840375 Si 1.5957424 -4.0240505 13.3550039 Si -1.5109526 -1.6128561 12.3632978 H -2.0647128 -4.7754017 11.3042420 H -2.0073498 -3.5879646 9.2254273 H -0.0716996 -4.7969248 9.9506215 H -2.2887769 -2.4668316 13.3218682 H -0.6393879 -0.7162510 13.1813912 H -2.5224873 -0.7210929 11.7005900 H 2.5508537 -4.7011622 14.2963584 H 0.6524971 -3.2368182 14.2093661 H 0.7766830 -5.1161738 12.7395708 H 4.8833837 -3.7577492 12.9923251 H 4.5634381 -3.4320865 10.6378988 H 4.6254438 -1.5445351 12.0992363 #Optimized Structure of [Fe(CO){N(SiH3)2}2]–, high-spin, He = -2652.4900168390 Fe 1.2007008 -2.6532730 11.0643383 C 1.8380471 -2.4520614 9.3999878 O 2.2553199 -2.3423372 8.2990670 N -0.7617224 -2.7799928 11.2179612 N 2.5695038 -2.9423669 12.4530612 Si -1.6139092 -2.3895161 9.7867092 Si 4.1302286 -3.3189553 11.8620085 Si 2.1873789 -2.7462323 14.1082726 Si -1.4851212 -3.3509584 12.6586054 H -3.1041689 -2.4710467 9.9829149 H -1.3437256 -0.9988422 9.3003737 H -1.2995646 -3.2974218 8.6374446 H 5.0987647 -3.6013362 12.9794004 H 4.1525503 -4.5362888 10.9898700 H 4.7425143 -2.2178189 11.0521373 H 3.2755639 -2.0464063 14.8705486 H 0.9475171 -1.9275296 14.2749882 H 1.9447374 -4.0309180 14.8466308 H -2.7420468 -4.1298937 12.3993997 H -0.5592457 -4.2586203 13.4032469 H -1.8704936 -2.2701362 13.6261885 #Optimized Structure of [Fe(CO){N(SiH3)2}2]–, low-spin, He = -2652.4796840940 Fe 1.0542525 -2.6231597 11.5868113 C 1.5879951 -1.5260670 10.4563716 O 1.9002660 -0.7229714 9.6356412 N -0.8247794 -2.6311808 11.5441652 N 2.6536400 -3.2857379 12.3617124 Si -1.4622919 -3.8210884 10.4803332 Si 4.2113322 -2.6787352 11.9869147 Si 2.2808760 -4.6526645 13.3318521 Si -1.6233514 -1.2078583 12.0763618 H -2.9038066 -4.0775959 10.8087726 H -1.4167175 -3.4424418 9.0306715 H -0.7509574 -5.1298719 10.6009617 H 5.2671696 -3.3604587 12.8093744 H 4.5878518 -2.8818124 10.5530356 H 4.3336767 -1.2133061 12.2528213 H 2.7523818 -4.5282878 14.7479984 H 0.7886121 -4.7806433 13.3617860 H 2.8292951 -5.9461355 12.8127646 H -3.0861841 -1.4768765 12.2774577 H -1.0941458 -0.7112754 13.3824818 H -1.5222856 -0.0637836 11.1148659