{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,11,22]],"date-time":"2025-11-22T10:57:47Z","timestamp":1763809067869,"version":"build-2065373602"},"reference-count":74,"publisher":"Wiley","issue":"45","license":[{"start":{"date-parts":[[2011,9,28]],"date-time":"2011-09-28T00:00:00Z","timestamp":1317168000000},"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":[[2011,11,4]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Phosphagermaallene Tip(<jats:italic>t<\/jats:italic>Bu)Ge\uf8feC\uf8fePMes* <jats:bold>1<\/jats:bold> (Tip=2,4,6\u2010triisopropylphenyl, Mes*=2,4,6\u2010tri\u2010<jats:italic>tert<\/jats:italic>\u2010butylphenyl) reacts with phenyl isocyanate and <jats:italic>tert<\/jats:italic>\u2010butyl isocyanate by a [2+2] cycloaddition that involves the Ge\uf8feC and C\uf8feO double bonds to afford 1\u2010oxa\u20102\u2010germacyclobutanes <jats:bold>2<\/jats:bold> and <jats:bold>3<\/jats:bold>. With <jats:italic>N<\/jats:italic>,<jats:italic>N\u2032<\/jats:italic>\u2010dicyclohexylcarbodiimide, a [2+2] cycloaddition is observed between the Ge\uf8feC and C\uf8feN unsaturations to lead to 1\u2010aza\u20102\u2010germacyclobutane <jats:bold>6<\/jats:bold> with exocyclic P\uf8feC and C\uf8feN double bonds. In sharp contrast, <jats:bold>1<\/jats:bold> reacts with phenyl isothiocyanate, ethyl isothiocyanate, and carbon disulfide according to a [3+2] cycloaddition that involves the whole Ge\uf8feC\uf8feP unit and the C\uf8feS double bond to give transient phosphagermacarbenes (PGeHCs) <jats:bold>11<\/jats:bold>, <jats:bold>12<\/jats:bold>, and <jats:bold>13<\/jats:bold>. These new PGeHCs undergo C\uf8ffH insertions into one <jats:italic>o<\/jats:italic>\u2010<jats:italic>t<\/jats:italic>Bu group of Mes* (in the case of <jats:bold>11<\/jats:bold> and <jats:bold>12<\/jats:bold>) or one <jats:italic>o<\/jats:italic>\u2010<jats:italic>i<\/jats:italic>Pr group of Tip (in the case of <jats:bold>13<\/jats:bold>) with formation of tricyclic compounds <jats:bold>8<\/jats:bold>, <jats:bold>9<\/jats:bold>, and <jats:bold>10<\/jats:bold>, respectively. The reaction mechanisms that involve <jats:bold>1<\/jats:bold> and the phenyl isocyanate and the phenyl isothiocyanate are described and their regioselectivity is explained by theoretical calculations.<\/jats:p>","DOI":"10.1002\/chem.201100281","type":"journal-article","created":{"date-parts":[[2011,9,28]],"date-time":"2011-09-28T09:40:16Z","timestamp":1317202816000},"page":"12763-12772","source":"Crossref","is-referenced-by-count":17,"title":["Versatile Stereoselective Cycloadditions between Heterocumulenes and Phosphagermaallene Tip(<i>t<\/i>Bu)Ge\uf8feC\uf8fePMes*: Experimental and Theoretical Investigations"],"prefix":"10.1002","volume":"17","author":[{"given":"Dumitru","family":"Ghereg","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Erwan","family":"Andr\u00e9","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Heinz","family":"Gornitzka","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jean","family":"Escudi\u00e9","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Fatima","family":"Ouhsaine","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Nathalie","family":"Saffon","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Karinne","family":"Miqueu","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jean\u2010Marc","family":"Sotiropoulos","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2011,9,28]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"For reviews on heteroallenes see"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr990013z"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0065-3055(00)46001-6"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0610086"},{"key":"e_1_2_6_5_2","first-page":"157","volume-title":"Multiple Bonds and Low Coordination in Phosphorus Chemistry","author":"Appel R.","year":"1990"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/a803041c"},{"key":"e_1_2_6_7_2","first-page":"1","volume-title":"The Chemistry of Organosilicon Compounds, Vol.\u20053","author":"Karni M.","year":"2001"},{"key":"e_1_2_6_8_2","unstructured":"\u00a0"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00077a069"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/om970246l"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1515\/MGMC.1999.22.3.147"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2001.1074"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/om100299w"},{"key":"e_1_2_6_14_2","unstructured":"Transient >Si\uf8feC\uf8feC< have been reported; see"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00003a022"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/om9701837"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja962591s"},{"key":"e_1_2_6_18_2","unstructured":"SiCN derivatives are better considered as silylene\u2013isocyanide complexes than azasilaallenes >Si\uf8feC\uf8feN\uf8ff (with the exception of the derivative reported by Kira in Ref.\u2005[4c] which represents allenic silaketenimine (azasilaallene) rather than such a donor\u2013acceptor complex). Due to the easy cleavage of the silicon\u2013carbon bond such compounds generally behave like silylenes and isocyanides:"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja963092u"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200204643"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja057917o"},{"key":"e_1_2_6_21_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19921040419"},{"key":"e_1_2_6_21_4","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199204371"},{"key":"e_1_2_6_22_2","unstructured":"\u00a0"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/om980152r"},{"key":"e_1_2_6_23_3","doi-asserted-by":"publisher","DOI":"10.1021\/om980555r"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/om970812c"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.1998.811"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3765(19990201)5:2<774::AID-CHEM774>3.0.CO;2-6"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/om9600248"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(01)01223-2"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/om801133h"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/om100233y"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201000747"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic1014913"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201003044"},{"key":"e_1_2_6_33_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201003044"},{"key":"e_1_2_6_34_2","unstructured":"Reviews:"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr940472u"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar000209h"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar960318p"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr0104330"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr900239n"},{"key":"e_1_2_6_40_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201000165"},{"key":"e_1_2_6_40_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201000165"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1080\/03086648708072843"},{"key":"e_1_2_6_42_2","unstructured":"\u00a0"},{"key":"e_1_2_6_43_2","doi-asserted-by":"publisher","DOI":"10.1016\/0010-8545(95)90222-8"},{"key":"e_1_2_6_44_2","doi-asserted-by":"publisher","DOI":"10.1515\/MGMC.2002.25.4.185"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0504607"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1002\/recl.19831020104"},{"key":"e_1_2_6_47_2","unstructured":"\u00a0"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)85751-2"},{"key":"e_1_2_6_48_3","first-page":"2361","volume":"52","author":"Kolodiazhnyi O. 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