{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2024,3,12]],"date-time":"2024-03-12T02:10:32Z","timestamp":1710209432411},"reference-count":47,"publisher":"American Chemical Society (ACS)","issue":"15","content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J. Phys. Chem. A"],"published-print":{"date-parts":[[2009,4,16]]},"DOI":"10.1021\/jp809525h","type":"journal-article","created":{"date-parts":[[2009,3,24]],"date-time":"2009-03-24T12:36:46Z","timestamp":1237898206000},"page":"3602-3609","source":"Crossref","is-referenced-by-count":0,"title":["Abstraction Reactions of Heavy Cyclobutenes with Carbon Tetrachloride. A Theoretical Study"],"prefix":"10.1021","volume":"113","author":[{"given":"Chi-Hui","family":"Chen","sequence":"first","affiliation":[{"name":"Department of Applied Chemistry, National Chiayi University, Chiayi 60004, Taiwan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jun","family":"Hsiao","sequence":"additional","affiliation":[{"name":"Department of Applied Chemistry, National Chiayi University, Chiayi 60004, Taiwan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ming-Der","family":"Su","sequence":"additional","affiliation":[{"name":"Department of Applied Chemistry, National Chiayi University, Chiayi 60004, Taiwan"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"316","published-online":{"date-parts":[[2009,3,24]]},"reference":[{"key":"ref1\/cit1a","doi-asserted-by":"crossref","first-page":"10303","DOI":"10.1021\/ja961913p","volume":"118","author":"Kira M.","year":"1996","journal-title":"J. Am. Chem. Soc."},{"key":"ref1\/cit1b","doi-asserted-by":"crossref","first-page":"2869","DOI":"10.1002\/(SICI)1521-3773(19981102)37:20<2869::AID-ANIE2869>3.0.CO;2-2","volume":"37","author":"Wiberg N.","year":"1998","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref1\/cit1c","doi-asserted-by":"crossref","first-page":"6012","DOI":"10.1021\/ja021480s","volume":"125","author":"Lee V. Y.","year":"2003","journal-title":"J. Am. Chem. Soc."},{"key":"ref2\/cit2a","first-page":"2834","volume":"23","author":"Lee V. Ya.","year":"2004","journal-title":"Organometallics"},{"key":"ref2\/cit2b","doi-asserted-by":"crossref","first-page":"1429","DOI":"10.1021\/cr0100300","volume":"103","author":"Lee V. Ya.","year":"2003","journal-title":"Chem. Rev."},{"key":"ref2\/cit2c","doi-asserted-by":"crossref","first-page":"6596","DOI":"10.1002\/anie.200604869","volume":"46","author":"Lee V. Ya.","year":"2007","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref3\/cit3a","doi-asserted-by":"crossref","first-page":"4758","DOI":"10.1021\/ja030662z","volume":"126","author":"Lee V. Y.","year":"2004","journal-title":"J. Am. Chem. Soc."},{"key":"ref3\/cit3b","doi-asserted-by":"crossref","first-page":"5768","DOI":"10.1021\/ja050938y","volume":"127","author":"Takanashi K.","year":"2005","journal-title":"J. Am. Chem. Soc."},{"key":"ref4\/cit4","doi-asserted-by":"crossref","first-page":"410","DOI":"10.1021\/ar6000473","volume":"40","author":"Lee V. Y.","year":"2007","journal-title":"Acc. Chem. Res."},{"key":"ref5\/cit5","unstructured":"See also"},{"key":"ref5\/cit5a","doi-asserted-by":"crossref","first-page":"2741","DOI":"10.1246\/bcsj.71.2741","volume":"71","author":"Iwamoto T.","year":"1998","journal-title":"Bull. Chem. Soc. Jpn."},{"key":"ref5\/cit5b","doi-asserted-by":"crossref","first-page":"1676","DOI":"10.1021\/ja002798s","volume":"123","author":"Kira M.","year":"2001","journal-title":"J. Am. Chem. Soc."},{"key":"ref6\/cit6a","doi-asserted-by":"crossref","first-page":"3098","DOI":"10.1103\/PhysRevA.38.3098","volume":"38","author":"Becke A. D.","year":"1988","journal-title":"Phys. Rev. A"},{"key":"ref6\/cit6b","doi-asserted-by":"crossref","first-page":"5648","DOI":"10.1063\/1.464913","volume":"98","author":"Becke A. D.","year":"1993","journal-title":"J. Chem. Phys."},{"key":"ref7\/cit7","doi-asserted-by":"crossref","first-page":"785","DOI":"10.1103\/PhysRevB.37.785","volume":"37","author":"Lee C.","year":"1988","journal-title":"Phys. Rev. B"},{"key":"ref8\/cit8a","unstructured":"aDunning, T. H., Jr.; Hay, P. J.InIModern Theoretical Chemistry;Schaefer, H. F., III., Ed.Plenum:New York, 1976; pp1\u221228."},{"key":"ref8\/cit8b","doi-asserted-by":"crossref","first-page":"270","DOI":"10.1063\/1.448799","volume":"82","author":"Hay P. J.","year":"1985","journal-title":"J. Chem. Phys."},{"key":"ref8\/cit8c","doi-asserted-by":"crossref","first-page":"284","DOI":"10.1063\/1.448800","volume":"82","author":"Hay P. J.","year":"1985","journal-title":"J. Chem. Phys."},{"key":"ref8\/cit8d","doi-asserted-by":"crossref","first-page":"299","DOI":"10.1063\/1.448975","volume":"82","author":"Hay P. J.","year":"1985","journal-title":"J. Chem. Phys."},{"key":"ref9\/cit9","doi-asserted-by":"crossref","first-page":"8111","DOI":"10.1021\/jp011945l","volume":"105","author":"Check C. E.","year":"2001","journal-title":"J. Phys. Chem. A"},{"key":"ref10\/cit10","unstructured":"For instance, see"},{"key":"ref10\/cit10a","doi-asserted-by":"crossref","first-page":"4846","DOI":"10.1021\/ic0303340","volume":"43","author":"Su M.-D.","year":"2004","journal-title":"Inorg. Chem."},{"key":"ref10\/cit10b","doi-asserted-by":"crossref","first-page":"2507","DOI":"10.1021\/om030675l","volume":"23","author":"Su M.-D.","year":"2004","journal-title":"Organometallics"},{"key":"ref10\/cit10c","doi-asserted-by":"crossref","first-page":"5877","DOI":"10.1002\/chem.200490080","volume":"10","author":"Su M.-D.","year":"2004","journal-title":"Eur. J. Chem."},{"key":"ref10\/cit10d","doi-asserted-by":"crossref","first-page":"6216","DOI":"10.1021\/jp060396m","volume":"110","author":"Tsai M.-L.","year":"2006","journal-title":"J Phys. Chem. B"},{"key":"ref11\/cit11","unstructured":"Frisch, M. J; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A.Gaussian, Inc.,Wallingford CT, 2003."},{"key":"ref12\/cit12b","doi-asserted-by":"crossref","first-page":"5840","DOI":"10.1021\/jo960387h","volume":"61","author":"Goller A.","year":"1996","journal-title":"J. Org. Chem."},{"key":"ref12\/cit12c","doi-asserted-by":"crossref","first-page":"6872","DOI":"10.1021\/ja983113f","volume":"121","author":"Nyulaszi L.","year":"1999","journal-title":"J. Am. Chem. Soc."},{"key":"ref12\/cit12d","doi-asserted-by":"crossref","first-page":"3819","DOI":"10.1021\/om980207p","volume":"17","author":"Tsutsui S.","year":"1998","journal-title":"Organometallics"},{"key":"ref12\/cit12e","doi-asserted-by":"crossref","first-page":"6553","DOI":"10.1016\/S0040-4039(01)01281-3","volume":"42","author":"Naruse Y.","year":"2001","journal-title":"Tetrahedron Lett."},{"key":"ref12\/cit12f","doi-asserted-by":"crossref","first-page":"2507","DOI":"10.1021\/om030675l","volume":"23","author":"Su M.-D.","year":"2004","journal-title":"Organometallics"},{"key":"ref13\/cit13","unstructured":"As suggested by reviewers, we also calculated the model system (D) by using the B3LYP\/6-31G(d) level of theory. Basically, our calculated bond lengths and bond angles are in agreement to within 0.083 \u00c5 and 3.2\u00b0, respectively, compared with the available experimental data. Besides these, we calculated its abstraction\u2212addition process (see eq1) with CCl4. Our theoretical findings suggest that its barrier height and reaction energy are 10.52 and \u221216.72 kcal\/mol, respectively. All these results are consistent with the present study based on the B3LYP\/LANL2DZdp method (see Table1). We thus feel confident that the current method (B3LYP\/LANL2DZdp) employed in this study should provide reliable information for the discussion of the nature of such abstraction\u2212addition reactions."},{"key":"ref14\/cit14","unstructured":"However, in case ofD,F, andG(X = Si, Sn, and Pb), the X\u2014Cl\u2032 bond lengths are almost identical. The reason for such phenomena could be the weak \u03c0\u2212\u03c3* effect. That is, the heavier central atom X has a larger atomic radius. This, in turn, can cause the weak \u03c0\u2212\u03c3* effect between the central X atom and chlorine, which makes X\u2014Cl\u2032 (X = Si, Sn, and Pb) bond lengths almost identical."},{"key":"ref15\/cit15","unstructured":"CompoundEhas a Ge\u2550Sn double bond; reactions at two atoms, Ge and Sn, are possible. According to our present calculations, however, we only found the Cl attack on the Ge atom and the CCl3attack on the Sn atom. The reason for this is could bethe electronic origin rather than the steric effect."},{"key":"ref16\/cit16","unstructured":"However, one reviewer indicates that barrier heights forD,E,F, andGare probably on the limit of the accuracy of the computational method used. It is believed that using the more sophisticated theoretical level would increase their barrier heights. Nevertheless, this is beyond the scope of the present work."},{"key":"ref17\/cit17","unstructured":"As suggested by one reviewer, when one Cl adds to one center of the X\u2550X bond to give Cl\u2014X\u2014X\u2022 and CCl3\u2022 radicals, it could be possible that the opposite face of the cyclobutene analogue reacts with another CCl4to yield a trans Cl\u2014X\/X\u2014Cl product. However, such a consideration needs at least two CCl4molecules to be involved in these model systems. As one can see, this would increase the complexity and difficulty of the questions we asked as well as enlarge the calculation systems that we studied in this work. We thus have no choice but to decide to use one CCl4molecule in our present model systems."},{"key":"ref18\/cit18","doi-asserted-by":"crossref","first-page":"7162","DOI":"10.1021\/jp0737698","volume":"111","author":"Chen C.-H.","year":"2007","journal-title":"J. Phys. Chem. A."},{"key":"ref19\/cit19","unstructured":"One reviewer mentioned that it could be possible yhatthese reactions progress via charged intermediates. However, such a case can yield many kinds of products. As suggested by the experimental work,(1)only one product has been found. We thus feel confident that no charged intermediates are involved in such reactions."},{"key":"ref20\/cit20","unstructured":"Although the second step was never analyzed theoretically in this manuscript, it is presumably assumed that Cl-abstraction path would be favored over the CCl3-abstraction one. The reason for this is the steric factor."},{"key":"ref21\/cit21","unstructured":"For details, see"},{"key":"ref21\/cit21a","volume-title":"Theoretical Aspects of Physical Organic Chemistry","author":"Shaik S.","year":"1992"},{"key":"ref21\/cit21b","volume-title":"Theoretical and Physical principles of Organic Reactivity","author":"Pross A.","year":"1995"},{"key":"ref21\/cit21c","doi-asserted-by":"crossref","first-page":"197","DOI":"10.1002\/9780470171943.ch4","volume":"15","author":"Shaik S.","year":"1985","journal-title":"Prog. Phys. Org. Chem."},{"key":"ref22\/cit22","unstructured":"For the first paper that originated the CM model, see"},{"key":"ref22\/cit22a","doi-asserted-by":"crossref","first-page":"3692","DOI":"10.1021\/ja00403a014","volume":"103","author":"Shaik S.","year":"1981","journal-title":"J. Am. Chem. Soc."},{"key":"ref22\/cit22b","doi-asserted-by":"crossref","first-page":"586","DOI":"10.1002\/(SICI)1521-3773(19990301)38:5<586::AID-ANIE586>3.0.CO;2-T","volume":"38","author":"Shaik S.","year":"1999","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref23\/cit23","doi-asserted-by":"crossref","first-page":"823","DOI":"10.1021\/jp031021t","volume":"108","author":"Su M.-D.","year":"2004","journal-title":"J. Phys. Chem. A."}],"container-title":["The Journal of Physical Chemistry A"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jp809525h","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,3,12]],"date-time":"2024-03-12T01:40:54Z","timestamp":1710207654000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/doi\/10.1021\/jp809525h"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2009,3,24]]},"references-count":47,"journal-issue":{"issue":"15","published-print":{"date-parts":[[2009,4,16]]}},"alternative-id":["10.1021\/jp809525h"],"URL":"https:\/\/doi.org\/10.1021\/jp809525h","relation":{},"ISSN":["1089-5639","1520-5215"],"issn-type":[{"value":"1089-5639","type":"print"},{"value":"1520-5215","type":"electronic"}],"subject":[],"published":{"date-parts":[[2009,3,24]]}}}