{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,29]],"date-time":"2026-07-29T21:31:11Z","timestamp":1785360671129,"version":"3.55.0"},"reference-count":110,"publisher":"Wiley","issue":"30","license":[{"start":{"date-parts":[[2014,6,5]],"date-time":"2014-06-05T00:00:00Z","timestamp":1401926400000},"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":[[2014,7,21]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>A convenient and robust synthesis of bis[<jats:italic>N<\/jats:italic>,<jats:italic>N<\/jats:italic>\u2032\u2010diisopropylbenzamidinato(\u2212)]silicon(<jats:sc>II<\/jats:sc>) (<jats:bold>1<\/jats:bold>), a donor\u2010stabilized silylene, has been developed (35\u2005g scale). To get further information about the reactivity profile of <jats:bold>1<\/jats:bold>, a series of oxidative addition reactions were studied. Treatment of <jats:bold>1<\/jats:bold> with PhSe\uf8ffSePh (Se\uf8ffSe bond activation), C<jats:sub>6<\/jats:sub>F<jats:sub>6<\/jats:sub> (C\uf8ffF activation), and CO<jats:sub>2<\/jats:sub> (C\uf8feO activation\/cycloaddition) yielded the neutral six\u2010coordinate silicon(<jats:sc>IV<\/jats:sc>) complexes <jats:bold>10<\/jats:bold>, <jats:bold>11<\/jats:bold>, and <jats:bold>13<\/jats:bold>, respectively. Treatment of <jats:bold>1<\/jats:bold> with N<jats:sub>2<\/jats:sub>O resulted in the formation of the dinuclear five\u2010coordinate silicon(<jats:sc>IV<\/jats:sc>) complex <jats:bold>12<\/jats:bold> (oxidative addition\/dimerization), which contains a four\u2010membered Si<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> ring. Compounds <jats:bold>10<\/jats:bold>\u2013<jats:bold>13<\/jats:bold> were characterized by NMR spectroscopic studies in the solid state and in solution and by crystal structure analyses. Silylene <jats:bold>1<\/jats:bold> is three\u2010coordinate in the solid state (from crystal structure analysis) and exists as the four\u2010coordinate isomer <jats:bold>1\u2032<\/jats:bold> in benzene solution (from computational studies). Based on state\u2010of\u2010the\u2010art relativistic DFT analyses, the four\u2010coordinate species <jats:bold>1\u2032<\/jats:bold> was demonstrated to be the thermodynamically favored isomer in benzene solution (favored by \u0394<jats:italic>G<\/jats:italic>=6.6\u2005kcal mol<jats:sup>\u22121<\/jats:sup> over the three\u2010coordinate species <jats:bold>1<\/jats:bold>). The reason for this was studied by bonding analyses of <jats:bold>1<\/jats:bold> and <jats:bold>1\u2032<\/jats:bold>. Furthermore, the <jats:sup>29<\/jats:sup>Si\u2005NMR chemical shifts of <jats:bold>1<\/jats:bold> and <jats:bold>1\u2032<\/jats:bold> were computed, and in the case of <jats:bold>1\u2032<\/jats:bold> it was analyzed how this NMR spectroscopic parameter is affected by solvation. These studies further supported the assumption that the silylene is four\u2010coordinate in solution.<\/jats:p>","DOI":"10.1002\/chem.201402483","type":"journal-article","created":{"date-parts":[[2014,6,5]],"date-time":"2014-06-05T15:51:59Z","timestamp":1401983519000},"page":"9319-9329","source":"Crossref","is-referenced-by-count":84,"title":["The Donor\u2010Stabilized Silylene Bis[<i>N<\/i>,<i>N<\/i>\u2032\u2010diisopropylbenzamidinato(\u2212)]silicon(II): Synthesis, Electronic Structure, and Reactivity"],"prefix":"10.1002","volume":"20","author":[{"given":"Konstantin","family":"Junold","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marco","family":"Nutz","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Johannes A.","family":"Baus","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christian","family":"Burschka","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"C\u00e9lia","family":"Fonseca\u2005Guerra","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"F. Matthias","family":"Bickelhaupt","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Reinhold","family":"Tacke","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2014,6,5]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"For selected reviews dealing with stable silicon(II) compounds see:"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/om7007869"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr900093s"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr100216y"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/om200017h"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/C1SC00757B"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201203072"},{"key":"e_1_2_6_8_2","unstructured":"For selected publications dealing with stable two\u2010coordinate silicon(II) compounds see:"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00085a088"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39950001931"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(96)06361-9"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1351\/pac199668040785"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3765(19980310)4:3<541::AID-CHEM541>3.0.CO;2-#"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9733999"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9925305"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja062928i"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2009.10.034"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201103656"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja301042u"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja301091v"},{"key":"e_1_2_6_21_2","unstructured":"For selected publications dealing with stable higher\u2010coordinate silicon(II) compounds see:"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19860980206"},{"key":"e_1_2_6_22_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198601641"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19901020311"},{"key":"e_1_2_6_23_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199002951"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/om950616a"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1099879"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200700398"},{"key":"e_1_2_6_26_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200700398"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200805749"},{"key":"e_1_2_6_27_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200805749"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200901766"},{"key":"e_1_2_6_28_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200901766"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200902431"},{"key":"e_1_2_6_29_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200902431"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9031049"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200902930"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/om100447g"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic9023162"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja910305p"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200903019"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201105639"},{"key":"e_1_2_6_36_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201105639"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201200632"},{"key":"e_1_2_6_37_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201200632"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201202277"},{"key":"e_1_2_6_38_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201202277"},{"key":"e_1_2_6_39_2","unstructured":"For selected publications dealing with stable higher\u2010coordinate silicon(II) compounds containing amidinato ligands see:"},{"key":"e_1_2_6_40_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200600647"},{"key":"e_1_2_6_40_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200600647"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja074019e"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic900204c"},{"key":"e_1_2_6_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9091374"},{"key":"e_1_2_6_44_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic101556s"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja205369h"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0dt01675f"},{"key":"e_1_2_6_47_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic2003035"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja210697p"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc31041d"},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2dt31578e"},{"key":"e_1_2_6_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic301543y"},{"key":"e_1_2_6_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/om3008794"},{"key":"e_1_2_6_53_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201203109"},{"key":"e_1_2_6_53_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201203109"},{"key":"e_1_2_6_54_2","unstructured":"\u00a0"},{"key":"e_1_2_6_55_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201202936"},{"key":"e_1_2_6_56_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic401954e"},{"key":"e_1_2_6_57_2","unstructured":"For recent publications dealing with higher\u2010coordinate silicon(IV) compounds see:"},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201000294"},{"key":"e_1_2_6_59_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201000152"},{"key":"e_1_2_6_60_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0dt00391c"},{"key":"e_1_2_6_61_2","doi-asserted-by":"publisher","DOI":"10.1039\/c1dt10898k"},{"key":"e_1_2_6_62_2","doi-asserted-by":"publisher","DOI":"10.1039\/C1DT11306B"},{"key":"e_1_2_6_63_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201101041"},{"key":"e_1_2_6_64_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201102815"},{"key":"e_1_2_6_65_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201200308"},{"key":"e_1_2_6_66_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic401698a"},{"key":"e_1_2_6_67_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201006265"},{"key":"e_1_2_6_67_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201006265"},{"key":"e_1_2_6_68_2","doi-asserted-by":"publisher","DOI":"10.1107\/S090744490804362X"},{"key":"e_1_2_6_69_2","unstructured":"\u00a0"},{"key":"e_1_2_6_70_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.1056"},{"key":"e_1_2_6_71_2","unstructured":"http:\/\/www.scm.com. For validation studies see:"},{"key":"e_1_2_6_72_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.20261"},{"key":"e_1_2_6_73_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.20653"},{"key":"e_1_2_6_74_2","unstructured":"\u00a0"},{"key":"e_1_2_6_75_2","volume-title":"Quantum Theory of Molecules and Solids, Vol.\u20054","author":"Slater J. C.","year":"1974"},{"key":"e_1_2_6_76_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevA.38.3098"},{"key":"e_1_2_6_77_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.37.785"},{"key":"e_1_2_6_78_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.464906"},{"key":"e_1_2_6_79_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.468265"},{"key":"e_1_2_6_80_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.21759"},{"key":"e_1_2_6_81_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.467943"},{"key":"e_1_2_6_82_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1097-461X(1996)57:3<281::AID-QUA2>3.0.CO;2-U"},{"key":"e_1_2_6_83_2","unstructured":"\u00a0"},{"key":"e_1_2_6_84_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.20078"},{"key":"e_1_2_6_85_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.20495"},{"key":"e_1_2_6_86_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.3382344"},{"key":"e_1_2_6_87_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.480688"},{"key":"e_1_2_6_88_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100002a024"},{"key":"e_1_2_6_89_2","unstructured":"\u00a0"},{"key":"e_1_2_6_90_2","doi-asserted-by":"publisher","DOI":"10.1039\/P29930000799"},{"key":"e_1_2_6_91_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100007a062"},{"key":"e_1_2_6_92_2","doi-asserted-by":"publisher","DOI":"10.1007\/s002140050457"},{"key":"e_1_2_6_93_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200700228"},{"key":"e_1_2_6_94_2","unstructured":"\u00a0"},{"key":"e_1_2_6_95_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp9820830"},{"key":"e_1_2_6_96_2","first-page":"1","volume-title":"Reviews in Computational Chemistry, Vol.\u200515","author":"Bickelhaupt F. M.","year":"2000"},{"key":"e_1_2_6_97_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108767307043930"},{"key":"e_1_2_6_98_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889811043202"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201402483","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201402483","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T14:41:28Z","timestamp":1760280088000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201402483"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2014,6,5]]},"references-count":110,"journal-issue":{"issue":"30","published-print":{"date-parts":[[2014,7,21]]}},"alternative-id":["10.1002\/chem.201402483"],"URL":"https:\/\/doi.org\/10.1002\/chem.201402483","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2014,6,5]]}}}