{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,12]],"date-time":"2026-03-12T14:28:13Z","timestamp":1773325693914,"version":"3.50.1"},"reference-count":62,"publisher":"Wiley","issue":"20","license":[{"start":{"date-parts":[[2003,10,10]],"date-time":"2003-10-10T00:00:00Z","timestamp":1065744000000},"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":[[2003,10,17]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Thermal\u2010 or SiO<jats:sub>2<\/jats:sub>\u2010induced reactions of the Michael adducts of 1,2\u2010aromatic dinucleophiles and alkynylchromium(<jats:sc>0<\/jats:sc>) carbene complexes, compounds <jats:bold>7<\/jats:bold>\u2013<jats:bold>10<\/jats:bold>, form different products in good yields depending on the nature of the aromatic dinucleophile used. Thus, 1,2\u2010diaminobenzene derivatives <jats:bold>7<\/jats:bold> and <jats:bold>8<\/jats:bold> rearrange to pentacarbonylchromium(<jats:sc>0<\/jats:sc>) isocyanide complexes <jats:bold>11, 12, 14<\/jats:bold>, and <jats:bold>15<\/jats:bold> in a process that occurs through bicyclic intermediates <jats:bold>24<\/jats:bold>. Adducts <jats:bold>9<\/jats:bold> derived from <jats:italic>o<\/jats:italic>\u2010aminophenol give 2,3\u2010dihydro\u20101,5\u2010benzoxazepine derivatives <jats:bold>17<\/jats:bold> by intramolecular 1,2\u2010addition, followed by protonation at the chromium center and reductive elimination. In contrast, base\u2010promoted addition of the phenolic hydroxy group in compound <jats:bold>9\u2009a<\/jats:bold> affords 3\u2010ethoxy\u20105\u2010phenyl\u20105,6\u2010dihydro\u20102<jats:italic>H<\/jats:italic>\u20101,6\u2010benzoxazocin\u20102\u2010one (<jats:bold>18<\/jats:bold>), together with the expected adduct <jats:bold>17\u2009a<\/jats:bold>. Compound <jats:bold>18<\/jats:bold> is formed by a nucleophilic addition to a CO ligand in a preformed carbene complex. This is a new example of the rare attack of a nucleophile on a CO ligand in a Fischer carbene complex. Adducts <jats:bold>10<\/jats:bold> form seven\u2010membered\u2010ring carbene complexes <jats:bold>19<\/jats:bold> and <jats:bold>20<\/jats:bold> by intramolecular aminolysis. In contrast, reaction of alkynyl carbene complexes with 1,8\u2010diaminonaphthalene under very mild conditions leads to 2\u2010substituted perimidines <jats:bold>33<\/jats:bold> together with the corresponding ethoxymethylmetal carbene complex <jats:bold>32<\/jats:bold> through an unprecedented fragmentation process in a formal retro\u2010Aumann reaction.<\/jats:p>","DOI":"10.1002\/chem.200305138","type":"journal-article","created":{"date-parts":[[2003,10,10]],"date-time":"2003-10-10T19:07:13Z","timestamp":1065812833000},"page":"4943-4953","source":"Crossref","is-referenced-by-count":25,"title":["Unexpected Reaction Pathways in the Reaction of Alkoxyalkynylchromium(<scp>0<\/scp>) Carbenes with Aromatic Dinucleophiles"],"prefix":"10.1002","volume":"9","author":[{"given":"Miguel A.","family":"Sierra","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mar\u00eda J.","family":"Manche\u00f1o","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Juan C.","family":"del Amo","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Israel","family":"Fern\u00e1ndez","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mar","family":"G\u00f3mez\u2010Gallego","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2003,10,10]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/om020827x"},{"key":"e_1_2_6_2_2","unstructured":"This is in agreement with the statement of the isolobal analogy principle. See:"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.211.4486.995"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19820941002"},{"key":"e_1_2_6_5_2","unstructured":"Reviews:"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)00837-8"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20001117)112:22<4124::AID-ANGE4124>3.0.CO;2-0"},{"key":"e_1_2_6_7_3","first-page":"3965","volume":"39","year":"2000","journal-title":"Angew. Chem. Int. Ed."},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0065-3055(08)60439-6"},{"key":"e_1_2_6_9_2","unstructured":"Selected reviews in the chemistry and synthetic applications of Fischer carbene complexes:"},{"key":"e_1_2_6_10_2","volume-title":"Transition Metal Carbene Complexes","author":"D\u00f6tz K. 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