{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,13]],"date-time":"2026-05-13T16:09:33Z","timestamp":1778688573181,"version":"3.51.4"},"reference-count":84,"publisher":"Wiley","issue":"8","license":[{"start":{"date-parts":[[2015,1,8]],"date-time":"2015-01-08T00:00:00Z","timestamp":1420675200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100000835","name":"University of Bath","doi-asserted-by":"crossref","id":[{"id":"10.13039\/501100000835","id-type":"DOI","asserted-by":"crossref"}]},{"DOI":"10.13039\/501100000266","name":"EPSRC","doi-asserted-by":"crossref","id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"crossref"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2015,2,16]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The electrophilic character of free diamidocarbenes (DACs) allows them to activate inert bonds in small molecules, such as NH<jats:sub>3<\/jats:sub> and P<jats:sub>4<\/jats:sub>. Herein, we report that metal coordinated DACs also exhibit electrophilic reactivity, undergoing attack by Zn and Cd dialkyl precursors to afford the migratory insertion products [(6\u2010MesDAC\u2010R)MR] (M=Zn, Cd; R=Et, Me; Mes=mesityl). These species were formed via the spectroscopically characterised intermediates [(6\u2010MesDAC)MR<jats:sub>2<\/jats:sub>], exhibiting barriers to migratory insertion which increase in the order MR<jats:sub>2<\/jats:sub> = ZnEt<jats:sub>2<\/jats:sub> &lt; ZnMe<jats:sub>2<\/jats:sub> &lt; CdMe<jats:sub>2<\/jats:sub>. Compound [(6\u2010MesDAC\u2010Me)CdMe] showed limited stability, undergoing deposition of Cd metal, by an apparent \u03b2\u2010H elimination pathway. These results raise doubts about the suitability of diamidocarbenes as ligands in catalytic reactions involving metal species bearing nucleophilic ligands (M\u2010R, M\u2010H).<\/jats:p>","DOI":"10.1002\/chem.201406406","type":"journal-article","created":{"date-parts":[[2015,1,8]],"date-time":"2015-01-08T15:44:33Z","timestamp":1420731873000},"page":"3215-3218","source":"Crossref","is-referenced-by-count":9,"title":["Unexpected Migratory Insertion Reactions of M(alkyl)<sub>2<\/sub> (M=Zn, Cd) and Diamidocarbenes"],"prefix":"10.1002","volume":"21","author":[{"given":"Lee R.","family":"Collins","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Gabriele","family":"Hierlmeier","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mary F.","family":"Mahon","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ian M.","family":"Riddlestone","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Michael K.","family":"Whittlesey","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2015,1,8]]},"reference":[{"key":"e_1_2_3_1_2","unstructured":"\u00a0"},{"key":"e_1_2_3_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/9783527609451"},{"key":"e_1_2_3_3_2","volume-title":"N\u2010Heterocyclic Carbenes in Transition Metal Catalysis (Topics in Organometallic Chemistry)","author":"Glorius F.","year":"2007"},{"key":"e_1_2_3_4_2","volume-title":"N\u2010Heterocyclic Carbenes: From Laboratory Curiosities to Efficient Synthetic Tools","author":"D\u00edez\u2010Gonz\u00e1lez 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CCDC\u20051034211 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre viawww.ccdc.cam.ac.uk\/data_request\/cif."},{"key":"e_1_2_3_51_2","unstructured":"For a comparison to other carbene stabilised Zn\u2013alkyl complexes see:"},{"key":"e_1_2_3_52_2","doi-asserted-by":"publisher","DOI":"10.1039\/c3dt51802g"},{"key":"e_1_2_3_53_2","doi-asserted-by":"publisher","DOI":"10.1021\/om500190c"},{"key":"e_1_2_3_54_2","doi-asserted-by":"publisher","DOI":"10.1002\/asia.201301268"},{"key":"e_1_2_3_55_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201105099"},{"key":"e_1_2_3_55_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201105099"},{"key":"e_1_2_3_56_2","unstructured":"The value ofrX\u2010raywas determined fromU=(4\u2009\u03c0(rX\u2010ray)3)\/3 (assuming a spherical geometry) in whichU=volume of the unit cell\/number of molecules in the unit cell. 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