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K[\n                    <jats:bold>1<\/jats:bold>\n                    ] reacts as a nucleophile with methyliodide to give [Rh(IPr)(dvtms)Me], a Rh(\u0399) compound with an exceptional trigonal\u2010pyramidal structure. Other haloalkanes abstract one electron from K[\n                    <jats:bold>1<\/jats:bold>\n                    ] to give the previously reported [Rh\n                    <jats:sup>0<\/jats:sup>\n                    (IPr)(dvtms)] complex. K[\n                    <jats:bold>1<\/jats:bold>\n                    ] also reacts with protonic acids and weak proton sources such as water and ketones to eventually give the rare tricoordinate 14\u2010electron complex [Rh\n                    <jats:sup>I<\/jats:sup>\n                    (IPr)(SiMe\n                    <jats:sub>2<\/jats:sub>\n                    OSiMe\n                    <jats:sub>2<\/jats:sub>\n                    CH\u00a0=\u00a0CH\n                    <jats:sub>2<\/jats:sub>\n                    )] with a Rh\u00a0\u2212Si bond. The 16\u2010electron complex [Rh\n                    <jats:sup>I<\/jats:sup>\n                    (IPr)(SiMe\n                    <jats:sub>2<\/jats:sub>\n                    OSiMe\n                    <jats:sub>2<\/jats:sub>\n                    CH\u00a0=\u00a0CH\n                    <jats:sub>2<\/jats:sub>\n                    )(H\n                    <jats:sub>2<\/jats:sub>\n                    C\u00a0=\u00a0CH\n                    <jats:sub>2<\/jats:sub>\n                    )] was characterized as an intermediate in this reaction. Furthermore, K[\n                    <jats:bold>1<\/jats:bold>\n                    ] runs up to five cycles of catalytic condensation of nonenolizable aldehydes to esters, such as\n                    <jats:italic>p<\/jats:italic>\n                    \u2010tolylaldehyde, before being fully converted into the inactive complex Rh(IPr)(\u03b7\n                    <jats:sup>3<\/jats:sup>\n                    \u2010C\n                    <jats:sub>3<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    <jats:italic>\n                      <jats:sup>p<\/jats:sup>\n                    <\/jats:italic>\n                    tolyl)(C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    )] with fragmentation of the diolefin dvtms. Computational studies have provided valuable insights into the reactivity patterns and behavior of this complex, including those of the rhodium(\u2212I)\/rhodium(I) catalytic cycle.\n                  <\/jats:p>","DOI":"10.1002\/chem.202501877","type":"journal-article","created":{"date-parts":[[2025,6,10]],"date-time":"2025-06-10T08:04:49Z","timestamp":1749542689000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["A Tour in the Chemistry of a Tricoordinate Rh(\u2212I) Complex"],"prefix":"10.1002","volume":"31","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7806-8959","authenticated-orcid":false,"given":"V\u00edctor","family":"Varela\u2010Izquierdo","sequence":"first","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica Instituto de S\u00edntesis Qu\u00edmica y Cat\u00e1lisis Homog\u00e9nea (ISQCH) CSIC\u2010Universidad de Zaragoza  Pedro Cerbuna 12, Facultad de Ciencias Zaragoza 50009 Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4500-1974","authenticated-orcid":false,"given":"Jos\u00e9 A.","family":"L\u00f3pez","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica Instituto de S\u00edntesis Qu\u00edmica y Cat\u00e1lisis Homog\u00e9nea (ISQCH) CSIC\u2010Universidad de Zaragoza  Pedro Cerbuna 12, Facultad de Ciencias Zaragoza 50009 Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7188-8014","authenticated-orcid":false,"given":"Miguel A.","family":"Ciriano","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica Instituto de S\u00edntesis Qu\u00edmica y Cat\u00e1lisis Homog\u00e9nea (ISQCH) CSIC\u2010Universidad de Zaragoza  Pedro Cerbuna 12, Facultad de Ciencias Zaragoza 50009 Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3306-0635","authenticated-orcid":false,"given":"Cristina","family":"Tejel","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica Instituto de S\u00edntesis Qu\u00edmica y Cat\u00e1lisis Homog\u00e9nea (ISQCH) CSIC\u2010Universidad de Zaragoza  Pedro Cerbuna 12, Facultad de Ciencias Zaragoza 50009 Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,6,18]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.3c00121"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2022.214941"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.9b00492"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201700397"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.5b00381"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr2004647"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic052110i"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.1c00737"},{"key":"e_1_2_8_9_1","first-page":"241","volume-title":"Advances of Organometallic Chemistry","author":"Rama R. 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