{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,17]],"date-time":"2026-10-17T18:41:08Z","timestamp":1792262468977,"version":"4.4.0"},"reference-count":61,"publisher":"Wiley","issue":"43","license":[{"start":{"date-parts":[[2026,9,8]],"date-time":"2026-09-08T00:00:00Z","timestamp":1788825600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,9,8]],"date-time":"2026-09-08T00:00:00Z","timestamp":1788825600000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2026,10,19]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    The calcium hydride, [(BDI)CaH]\n                    <jats:sub>2<\/jats:sub>\n                    (BDI = HC{C(Me)NDipp}\n                    <jats:sub>2<\/jats:sub>\n                    , where Dipp = 2,6\u2010\n                    <jats:italic>i\u2010<\/jats:italic>\n                    Pr\n                    <jats:sub>2<\/jats:sub>\n                    C\n                    <jats:sub>6<\/jats:sub>\n                    H\n                    <jats:sub>3<\/jats:sub>\n                    ), reacts with Zn\n                    <jats:italic>t<\/jats:italic>\n                    \u2010Bu\n                    <jats:sub>2<\/jats:sub>\n                    to form the monomeric and toluene\u2010stabilised calcium dialkyl(hydrido)zincate, [(BDI)Ca\u2010\u03bc\u2010H\u2010Zn(\n                    <jats:italic>t<\/jats:italic>\n                    \u2010Bu)\n                    <jats:sub>2<\/jats:sub>\n                    (\u03b7\n                    <jats:sup>6<\/jats:sup>\n                    \u2010C\n                    <jats:sub>7<\/jats:sub>\n                    H\n                    <jats:sub>8<\/jats:sub>\n                    )]. When treated with dialkyl ethers, this compound initiates a sequence of twofold ether deprotonation and dealkylation by alkene extrusion, from which the resultant oxide dianion is sequestered as a\n                    <jats:italic>tert<\/jats:italic>\n                    \u2010butoxide anion. Through a combination of experiment and theory, this completely selective C\u2500O bond forming process is deduced to result from the formation of incipient calcium\n                    <jats:italic>tert<\/jats:italic>\n                    \u2010butyl and hydride intermediates, and subsequent tertiary carbenium ion generation enabled by reduction of Zn(II) to elemental zinc. The overall transformation, therefore, may be rationalised as a consequence of latent extreme basicity in harness with a cooperative redox process that is intrinsic to the combination of dissimilar constituent metals.\n                  <\/jats:p>","DOI":"10.1002\/anie.9268230","type":"journal-article","created":{"date-parts":[[2026,9,9]],"date-time":"2026-09-09T04:29:37Z","timestamp":1788928177000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Dialkyl Ethers and Sacrificial Zinc: Oxide Synthons for Calcium\n                    <i>tert<\/i>\n                    \u2010Butoxide Formation"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1886-4483","authenticated-orcid":false,"given":"Kyle G.","family":"Pearce","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Bath  Bath UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0006-8486-4149","authenticated-orcid":false,"given":"Agust\u00edn","family":"Morales","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Bath  Bath UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9784-9649","authenticated-orcid":false,"given":"Michael S.","family":"Hill","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Bath  Bath UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4924-2890","authenticated-orcid":false,"given":"Claire L.","family":"McMullin","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Bath  Bath UK"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,9,8]]},"reference":[{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/om900088z"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/jlac.19505670112"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198709721"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/op500161b"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/om960642o"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022\u2010328X(00)87484\u20107"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00969a007"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.197007631"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo01361a007"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/b109604d"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.667"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202514283"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1039\/jr9630000577"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00964a012"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41570\u2010023\u201000548\u20100"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2007.10.023"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1039\/a703972g"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200503452"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.inoche.2005.09.030"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201603786"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.aao5923"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201809833"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.8b00743"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201801869"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.1c00278"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202200305"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/advs.202304765"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1039\/D4CC02930E"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1039\/D5DT00958H"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5c10735"},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.5c05335"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8DT03124J"},{"key":"e_1_2_7_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.9b00493"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CC04083D"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.202000264"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0DT03415K"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1DT01532J"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/om010301x"},{"key":"e_1_2_7_40_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200701255"},{"key":"e_1_2_7_41_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200701028"},{"key":"e_1_2_7_42_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6DT04659B"},{"key":"e_1_2_7_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b04926"},{"key":"e_1_2_7_44_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2021.131931"},{"key":"e_1_2_7_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja036020t"},{"key":"e_1_2_7_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.7b00287"},{"key":"e_1_2_7_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/om100106e"},{"key":"e_1_2_7_48_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo971176v"},{"key":"e_1_2_7_49_1","unstructured":"Although the complexity and semi\u2010heterogeneity of the reaction mitigated against reliable kinetic monitoring consistent with the operation of a significant kinetic isotope effect it is notable that the reaction of1withd10\u2010diethyl ether required several days to achieve completion."},{"key":"e_1_2_7_50_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201000164"},{"key":"e_1_2_7_51_1","unstructured":"IntermediateBis 0.3\u00a0kcal mol\u22121higher in corrected free energy thanTS(A\u2010B)as depicted in Figure 4 however the electronic energy for the optimisedBlies 0.7\u00a0kcal mol\u22121belowTS(A\u2010B).The addition of a dispersion correction is what inverts this energy order to give that shown in Figure 4."},{"key":"e_1_2_7_52_1","unstructured":"While ether fragmentation by the processes summarised in Scheme 1a are generally assumed to occur by concerted E2 alkene elimination (see reference 2b) the identification of the zinc\u2010 and calcium\u2010stabilised alkyl 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