{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T12:04:44Z","timestamp":1789473884579,"version":"build-2803163510"},"reference-count":63,"publisher":"American Chemical Society (ACS)","issue":"16","license":[{"start":{"date-parts":[[2007,7,11]],"date-time":"2007-07-11T00:00:00Z","timestamp":1184112000000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2007,7,11]],"date-time":"2007-07-11T00:00:00Z","timestamp":1184112000000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2007,7,11]],"date-time":"2007-07-11T00:00:00Z","timestamp":1184112000000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2007,8,6]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Treatment of [RhCl(\u03b74-diene)]2 (diene = nbd, cod) with the N-heterocyclic ligands 2,2\u2018-bipyridine (bpy), 4,4\u2018-dimethyl-2,2\u2018-bipyridine (Me2bpy), 1,10-phenanthroline (phen), and pyridine (py) followed by addition of Cs[arachno-6-SB9H12] affords the corresponding salts, [Rh(\u03b74-diene)(L2)][SB9H12] [diene = cod, L2 = bpy (1), Me2bpy (3), phen (5), (py)2 (7); diene = nbd, L2 = bpy (2), Me2bpy (4), phen (6), (py)2 (8)]. These compounds are characterized by NMR spectroscopy and mass spectrometry, and in addition, the cod\u2212Rh species 1 and 3 are studied by X-ray diffraction analysis. These saltlike reagents are stable in the solid state, but in solution the rhodium(I) cations, [Rh(\u03b74-diene)(L2)]+, react with the polyhedral anion [SB9H12]- leading to a chemistry that is controlled by the d8 transition element chelates. The nbd\u2212Rh(I) complexes react faster than the cod\u2212Rh(I) counterparts, leading, depending on the conditions, to the synthesis of new rhodathiaboranes of general formulas [8,8-(L2)-nido-8,7-RhSB9H10] [L2 = bpy (9), Me2bpy (10), phen (11), (py)2 (12)] and [8,8-(L2)-8-(L\u2018)-nido-8,7-RhSB9H10] [L\u2018 = PPh3, L2 = bpy (13), Me2bpy (14), phen (15); L\u2018 = NCCH3, L2 = bpy (16), Me2bpy (17), phen (18)]. Compound 13 is characterized by X-ray diffraction analysis confirming the 11-vertex nido-structure of the rhodathiaborane analogues 14\u221218. In dichloromethane, 1 and 3 yield mixtures that contain the 11-vertex rhodathiaboranes 9 and 10 together with new species. In contrast, the cod\u2212Rh(I) reagent 5 affords a single compound, which is proposed to be an organometallic rhodium complex bound exo-polyhedrally to the thiaborane cage. In the presence of H2(g) and stoichiometric amounts of PPh3, the cod\u2212Rh(I) reagents, 1, 3, and 5, afford the salts [Rh(H)2(L2)(PPh3)2][SB9H12] [L2 = bpy (19), Me2bpy (20), phen (21)]. Similarly, in an atmosphere of CO(g) and in the presence of PPh3, compounds 1\u22126 afford [Rh(L2)(PPh3)2(CO)][SB9H12] (L2 = bpy (22), Me2bpy (23), phen (24)]. The structures of 19 and 24 are studied by X-ray diffraction analysis. The five-coordinate complexes [Rh(L2)(PPh3)2(CO)]+ undergo PPh3 exchange in a process that is characterized as dissociative. The observed differences in the reactivity of the nbd\u2212Rh(I) salts versus the cod\u2212Rh(I) analogues are rationalized on the basis of the higher kinetic lability of the nbd ligand and its faster hydrogenation relative to the cod diene.<\/jats:p>","DOI":"10.1021\/ic700648z","type":"journal-article","created":{"date-parts":[[2007,7,11]],"date-time":"2007-07-11T09:00:27Z","timestamp":1184144427000},"page":"6811-6826","source":"Crossref","is-referenced-by-count":19,"title":["Square-Planar Rhodium(I) Complexes Partnered with\n[\n                    <i>arachno<\/i>\n                    -6-SB9H12]-:\u2009 A Route toward the Synthesis of New\nRhodathiaboranes and Organometallic\/Thiaborane Salts"],"prefix":"10.1021","volume":"46","author":[{"given":"\u00c1lvaro","family":"\u00c1lvarez","sequence":"first","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica, Instituto Universitario de Cat\u00e1lisis Homog\u00e9nea, Instituto de Ciencia de Materiales de Arag\u00f3n, Universidad de Zaragoza-Consejo Superior de Investigaciones Cient\u00edficas, 50009-Zaragoza, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ram\u00f3n","family":"Mac\u00edas","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica, Instituto Universitario de Cat\u00e1lisis Homog\u00e9nea, Instituto de Ciencia de Materiales de Arag\u00f3n, Universidad de Zaragoza-Consejo Superior de Investigaciones Cient\u00edficas, 50009-Zaragoza, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mar\u00eda Jos\u00e9","family":"Fabra","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica, Instituto Universitario de Cat\u00e1lisis Homog\u00e9nea, Instituto de Ciencia de Materiales de Arag\u00f3n, Universidad de Zaragoza-Consejo Superior de Investigaciones Cient\u00edficas, 50009-Zaragoza, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Maria L.","family":"Mart\u00edn","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica, Instituto Universitario de Cat\u00e1lisis Homog\u00e9nea, Instituto de Ciencia de Materiales de Arag\u00f3n, Universidad de Zaragoza-Consejo Superior de Investigaciones Cient\u00edficas, 50009-Zaragoza, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fernando J.","family":"Lahoz","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica, Instituto Universitario de Cat\u00e1lisis Homog\u00e9nea, Instituto de Ciencia de Materiales de Arag\u00f3n, Universidad de Zaragoza-Consejo Superior de Investigaciones Cient\u00edficas, 50009-Zaragoza, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Luis A.","family":"Oro","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica, Instituto Universitario de Cat\u00e1lisis Homog\u00e9nea, Instituto de Ciencia de Materiales de Arag\u00f3n, Universidad de Zaragoza-Consejo Superior de Investigaciones Cient\u00edficas, 50009-Zaragoza, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2007,7,11]]},"reference":[{"key":"2026091506564626500_elcit1","doi-asserted-by":"publisher","first-page":"1832","DOI":"10.1021\/om061053d","volume":"26","author":"Deng","year":"2007","journal-title":"Organometallics"},{"key":"2026091506564626500_elcit2","doi-asserted-by":"publisher","first-page":"5758","DOI":"10.1002\/chem.200500280","volume":"11","author":"Wang","year":"2005","journal-title":"Chem.Eur. 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