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The IR-spectroscopic and X-ray crystallographic data of 2 highlight the strong \u03c0-donor properties of the DBB ligand. The reaction of 1 with [M\u00ad(nbe)2] (M = Pd, Pt; nbe = norbornene) yields the unique zerovalent heavier group 10 arene pogo-stick complexes [(\u03b76-DBB)\u00adM\u00ad(nbe)] (3-M), isolated as dark-purple and black crystalline solids, respectively. 3-Pd and 3-Pt show strong near-IR (NIR) absorptions at 835 and 904 nm, respectively. Time-dependent density functional theory (TD-DFT) calculations show that these result from the S0\u2192S1 excitation, which corresponds to a transfer of electron density from a metal d orbital aligned with the z direction (dxz or dyz) to a d orbital located in the xy plane (dxy or dx2\u2013y2), with the redshift for 3-Pt resulting from the higher spin-orbit coupling (SOC). In complex 2, electron donation from the nickel center into the carbonyl 2\u03c0* orbital destabilizes the DBB\u00b7\u00b7\u00b7Ni interaction, resulting in an absorption at a higher energy. Complexes 2 and 3-M react with [Fe\u00ad(CO)5] to yield the doubly CO-bridged M(0)\u2192Fe(0) (M = Ni, Pd, Pt) metal-only Lewis pairs (MOLPs) 4-M as black (M = Ni, Pt) and dark-turquoise (M = Pd) crystalline solids. Furthermore, 3-Pt undergoes oxidative Sn\u2013H addition with Ph3SnH to yield the corresponding Pt\u00ad(II) stannyl hydride, [(\u03b76-DBB)\u00adPtH\u00ad(SnPh3)] (5).<\/jats:p>","DOI":"10.1021\/jacs.3c08323","type":"journal-article","created":{"date-parts":[[2023,10,2]],"date-time":"2023-10-02T16:31:54Z","timestamp":1696264314000},"page":"22222-22231","source":"Crossref","is-referenced-by-count":7,"title":["Synthesis\nand Reactivity of Highly Electron-Rich Zerovalent\nGroup 10 Diborabenzene Pogo-Stick Complexes"],"prefix":"10.1021","volume":"145","author":[{"given":"Maximilian","family":"Dietz","sequence":"first","affiliation":[{"name":"Julius-Maximilians-Universita\u0308t Wu\u0308rzburg , , ,","place":["Am Hubland, , Wu\u0308rzburg, Germany, 97074"]},{"name":"Julius-Maximilians-Universita\u0308t Wu\u0308rzburg , , , ,","place":["Am Hubland, Wu\u0308rzburg, Germany, 97074"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1449-5932","authenticated-orcid":true,"given":"Merle","family":"Arrowsmith","sequence":"additional","affiliation":[{"name":"Julius-Maximilians-Universita\u0308t Wu\u0308rzburg , , ,","place":["Am Hubland, , Wu\u0308rzburg, Germany, 97074"]},{"name":"Julius-Maximilians-Universita\u0308t Wu\u0308rzburg , , , ,","place":["Am Hubland, Wu\u0308rzburg, Germany, 97074"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5523-3624","authenticated-orcid":true,"given":"Lukas","family":"Endres","sequence":"additional","affiliation":[{"name":"Julius-Maximilians-Universita\u0308t Wu\u0308rzburg , , ,","place":["Am Hubland, , Wu\u0308rzburg, Germany, 97074"]},{"name":"Julius-Maximilians-Universita\u0308t Wu\u0308rzburg , , , ,","place":["Am Hubland, Wu\u0308rzburg, Germany, 97074"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Valerie","family":"Paprocki","sequence":"additional","affiliation":[{"name":"Julius-Maximilians-Universita\u0308t Wu\u0308rzburg , , ,","place":["Am Hubland, , Wu\u0308rzburg, Germany, 97074"]},{"name":"Julius-Maximilians-Universita\u0308t Wu\u0308rzburg , , , ,","place":["Am Hubland, Wu\u0308rzburg, Germany, 97074"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3057-389X","authenticated-orcid":true,"given":"Bernd","family":"Engels","sequence":"additional","affiliation":[{"name":"Julius-Maximilians-Universita\u0308t Wu\u0308rzburg , , Emil-Fischer-Strasse 42 , ,","place":["Wu\u0308rzburg, Germany, 97074"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9264-1726","authenticated-orcid":true,"given":"Holger","family":"Braunschweig","sequence":"additional","affiliation":[{"name":"Julius-Maximilians-Universita\u0308t Wu\u0308rzburg , , ,","place":["Am Hubland, , Wu\u0308rzburg, Germany, 97074"]},{"name":"Julius-Maximilians-Universita\u0308t Wu\u0308rzburg , , , ,","place":["Am Hubland, Wu\u0308rzburg, Germany, 97074"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2023,10,2]]},"reference":[{"key":"2026081707182678900_cit1","doi-asserted-by":"publisher","DOI":"10.3390\/inorganics9070055","article-title":"Arene-Osmium\u00ad(II) Complexes in Homogeneous Catalysis","volume":"9","author":"Crochet","year":"2021","journal-title":"Inorganics"},{"key":"2026081707182678900_cit2","doi-asserted-by":"publisher","first-page":"6512","DOI":"10.1002\/ejoc.202000752","article-title":"Applications\nof Chiral Cyclopentadienyl\n(Cpx) Metal Complexes in Asymmetric Catalysis","volume":"2020","author":"Shaaban","year":"2020","journal-title":"Eur. 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