{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,8]],"date-time":"2026-01-08T23:03:33Z","timestamp":1767913413375,"version":"3.49.0"},"reference-count":52,"publisher":"Wiley","issue":"34","license":[{"start":{"date-parts":[[2009,8,5]],"date-time":"2009-08-05T00:00:00Z","timestamp":1249430400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2009,8,24]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Insertion reactions of dimethylsilylene (Me<jats:sub>2<\/jats:sub>Si:) into the silicon\u2013chlorine bond of various substituted chlorosilanes have been computationally studied by using DFT calculations with a 6\u201031++G(d,p) basis set. All of the insertions investigated herein were exothermic (more than 40\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>) and proceeded via three\u2010membered cyclic transition states (TS) with one substituent of a chlorosilane in the ring plane and two other substituents out of the plane. Among the two possible concerted insertion pathways, the pathway via a TS with a silylene lone\u2010pair orbital approaching a chlorosilane silicon atom was preferred. Important nucleophilic interactions of silylene lone\u2010pair orbitals with anti\u2010bonding \u03c3 orbitals of Si\uf8ffY (in plane) were supported by carrying out a natural bond orbital (NBO) analysis of the reaction. A radical pathway through the initial abstraction of chlorine from chlorosilane by the silylene cannot compete with the preferred concerted pathway. Systematic calculations for SiMe<jats:sub>2<\/jats:sub> insertion into various chlorosilanes (YR<jats:sub>2<\/jats:sub>SiCl; Y (in\u2010plane substituent)=H, Me, NH<jats:sub>2<\/jats:sub>, OH, F, SiH<jats:sub>3<\/jats:sub>, PH<jats:sub>2<\/jats:sub>, SH and Cl; R (out\u2010of\u2010plane substituent)=H, Me, <jats:italic>i<\/jats:italic>Pr and <jats:italic>t<\/jats:italic>Bu) have revealed remarkable substituent effects on activation free energies (\u0394<jats:italic>G<\/jats:italic><jats:sup>\u2260<\/jats:sup>). In\u2010plane (Y) substituent effects were mostly electronic. Electron\u2010withdrawing substituents accelerate the insertion through enhanced nucleophilic interaction between silylene lone\u2010pair orbitals with the \u03c3*(Si\uf8ffY) orbital at the TS. The \u0394<jats:italic>G<\/jats:italic><jats:sup>\u2260<\/jats:sup> values correlate with the \u03c3<jats:sub>I<\/jats:sub> constants as a scale of the inductive effect of Y. Out\u2010of\u2010plane (R) substituent effects are mainly steric, and bulky substituents increase the activation free energy . Correlation of the \u0394<jats:italic>G<\/jats:italic><jats:sup>\u2260<\/jats:sup> values with Taft\u2019s steric substituent constants (E<jats:sub>s<\/jats:sub>) was observed. There was no significant difference in the out\u2010of\u2010plane substituent effects between the electron\u2010withdrawing Cl and the electron\u2010donating Me groups.<\/jats:p>","DOI":"10.1002\/chem.200901285","type":"journal-article","created":{"date-parts":[[2009,8,5]],"date-time":"2009-08-05T08:09:27Z","timestamp":1249459767000},"page":"8605-8612","source":"Crossref","is-referenced-by-count":14,"title":["Remarkable Substituent Effects on the Activation Energy of Silylene Insertion into Silicon\u2013Chlorine Bonds"],"prefix":"10.1002","volume":"15","author":[{"given":"Zheng","family":"Xu","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Juan","family":"Jin","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Zhifang","family":"Li","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Huayu","family":"Qiu","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jianxiong","family":"Jiang","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Guoqiao","family":"Lai","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mitsuo","family":"Kira","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2009,8,19]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"For reviews of the reactions of silylenes see"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/0470857250.ch43"},{"key":"e_1_2_6_3_2","first-page":"59","volume-title":"The Chemistry of Organic Silicon Compounds, Vol.\u20051","author":"Apeloig Y.","year":"1989"},{"key":"e_1_2_6_4_2","first-page":"229","volume-title":"Reactive Intermediates, Vol. 1","author":"Gaspar P. P.","year":"1978"},{"key":"e_1_2_6_5_2","first-page":"335","volume-title":"Reactive Intermediates, Vol.\u20052","author":"Gaspar P. P.","year":"1981"},{"key":"e_1_2_6_6_2","first-page":"333","volume-title":"Reactive Intermediates, Vol.\u20053","author":"Gaspar P. P.","year":"1985"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-1-4613-3192-6_4"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19690811303"},{"key":"e_1_2_6_8_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.196904691"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/b617844h"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(95)05762-E"},{"key":"e_1_2_6_11_2","unstructured":"\u00a0"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3765(19980515)4:5<852::AID-CHEM852>3.0.CO;2-7"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(01)01451-6"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9925305"},{"key":"e_1_2_6_14_3","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.80.258"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature01380"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1023\/B:SILC.0000046709.84243.6b"},{"key":"e_1_2_6_17_2","unstructured":"\u00a0"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0741473"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja8093313"},{"key":"e_1_2_6_20_2","unstructured":"For theoretical studies on the insertion of silylenes into Si\uf8ffH bonds see:"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100121a017"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp9916440"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200400413"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp710740a"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1002\/0470857269.ch1"},{"key":"e_1_2_6_26_2","unstructured":"\u00a0"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar50038a003"},{"key":"e_1_2_6_28_2","volume-title":"Frontier Orbital and Organic Chemical Reactions","author":"Fleming I.","year":"1976"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/om900116z"},{"key":"e_1_2_6_30_2","unstructured":"For experimental see:"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2001.1102"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja012389b"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja052584g"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp044458p"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic7012446"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200601736"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp055885l"},{"key":"e_1_2_6_38_2","unstructured":"Gaussian\u200503 Revision D.01 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman J.\u2005A. Montgomery \u2005Jr. T. Vreven K.\u2005N. Kudin J.\u2005C. Burant J.\u2005M. Millam S.\u2005S. Iyengar J. Tomasi V. Barone M. Mennucci M. Cossi G. Scalmani N. Rega G.\u2005A. Peterssom M. Nakatsuji M. Hoda M. Ehara K.Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai M. Klene X. Li J.\u2005E. Knox H.\u2005P. Hratchian J.\u2005B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R.\u2005E. Stratmann O. Yazyev A.\u2005J. Austin R. Cammi C. Pomelli J.\u2005W. Ochterski P.\u2005Y. Ayala K. Morokuma G.\u2005A. Voth P. Salvador J.\u2005J. Dannenberg V.\u2005G. Zakrzewski S. Dapprich A.\u2005D. Daniels M.\u2005C. Strain O. Farkas D.\u2005K. Malick A.\u2005D. Rabuck K. Raghavachari J.\u2005B. Foresman J.\u2005V. Ortiz Q. Cui A.\u2005G. Baboul S. Clifford J. Cioslowski B.\u2005B. Stefanov G. Liu A. Liashenko P. Piskorz I. Komaromi R.\u2005L. Martin D.\u2005J. Fox M.\u2005T. Keith A. Al\u2010Laham C.\u2005Y. Peng A. Nanayakkara M. Challacombe P.\u2005M.\u2005W. Gill B. Johnson W. Chen M.\u2005W. Wong C. Gonzalez J.\u2005A. Pople Gaussian Inc. Wallingford CT 2004."},{"key":"e_1_2_6_39_2","unstructured":"To test the dependence of the activation parameters on the calculation methods we have performed similar calculations for several reactions at the MP2\/6\u201031++G(d p) and BMK\/6\u201031++G(d p) levels. The absolute values of the activation parameters are rather dependent on the methods but the substituent effects are fairly parallel to those found by the calculations using the B3LYP method. See reference\u2005[9] for the details."},{"key":"e_1_2_6_40_2","doi-asserted-by":"publisher","DOI":"10.1039\/b007902m"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01607a027"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4020(68)88057-3"},{"key":"e_1_2_6_43_2","unstructured":"As shown in Table\u20052 and Scheme\u20052 the activation parameters and the geometrical parameters calculated here forTS2\u2019are in reasonable agreement with those reported by Becerra et\u2005al. in which the geometry and energies were determined at the B3LYP\/6\u201031G(d) and G2(MP2 SVP)\/\/B3LYP\/6\u201031G(d) levels.[7d]"},{"key":"e_1_2_6_44_2","unstructured":"The chlorine abstraction by a silyl radical from a chlorosilane should be almost thermo\u2010neutral and hence less favourable than the highly exothermic abstraction from the chloroalkane. The positive \u0394Gvalue for step\u20051 could be ascribed to the loss of the stabilisation of the silylene during chlorine abstraction."},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00002a004"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01132a049"},{"key":"e_1_2_6_47_2","unstructured":"\u0394G\u2260values are taken from Tables\u20053\u20136. The Esvalue for H Me iPr tBu and Cl are 1.24 0 \u22120.47 \u22121.54 and 0.18 respectively which were taken from reference\u2005[19]."},{"key":"e_1_2_6_48_2","unstructured":"\u00a0"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1039\/f19767201912"},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00146a034"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.200901285","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.200901285","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/chem.200901285","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.200901285","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T09:31:34Z","timestamp":1760261494000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.200901285"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2009,8,19]]},"references-count":52,"journal-issue":{"issue":"34","published-print":{"date-parts":[[2009,8,24]]}},"alternative-id":["10.1002\/chem.200901285"],"URL":"https:\/\/doi.org\/10.1002\/chem.200901285","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2009,8,19]]}}}