{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T12:04:02Z","timestamp":1789473842109,"version":"build-2803163510"},"reference-count":97,"publisher":"American Chemical Society (ACS)","issue":"16","license":[{"start":{"date-parts":[[2007,7,3]],"date-time":"2007-07-03T00:00:00Z","timestamp":1183420800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2007,7,3]],"date-time":"2007-07-03T00:00:00Z","timestamp":1183420800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2007,7,3]],"date-time":"2007-07-03T00:00:00Z","timestamp":1183420800000},"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>Reaction of Mo2(pyphos)4 (1) with [MCl(CO)2]2 (M = Ir and Rh) afforded linear tetranuclear complexes of a formula Mo2M2(CO)2(Cl)2(pyphos)4 (2, M = Ir; 3, M = Rh). X-ray diffraction studies confirmed that two \u201cMCl(CO)\u201d fragments are introduced into both axial sites of the Mo2 core in 1 and coordinated by two PPh2 groups in a trans fashion, thereby forming a square-planar geometry around each M(I) metal. Treatment of 2 and 3 with an excess amount of t BuNC and XylNC induced dissociation of the carbonyl and chloride ligands to yield the corresponding dicationic complexes [Mo2M2(pyphos)4(t BuNC)4](Cl)2 (5a, M = Ir; 6a, M = Rh) and [Mo2M2(pyphos)4(XylNC)4](Cl)2 (7, M = Ir; 8, M = Rh). Their molecular structures were characterized by spectroscopic data as well as X-ray diffraction studies of BPh4 derivatives [Mo2M2(pyphos)4(t BuNC)4](BPh4)2 (5b, M = Ir; 6c, M = Rh), which confirmed that there is no direct \u03c3-bonding interaction between the M(I) atom and the Mo2 core. The M(I) atom in 5 and 6 can be oxidized by either 2 equiv of [Cp2Fe][PF6] or an equimolar amount of I2 to afford Mo(II)2M(II)2 complexes, [Mo2M2(X)2(t BuNC)4(pyphos)4]2+ in which two Mo\u2212M(II) single bonds are formed and the bond order of the Mo\u2212Mo moiety has been decreased to three. The Ir(I) complex 5a reacted not only with methyl iodide but also with dichloromethane to afford the 1,4-oxidative addition products [Mo2Ir2(CH3)(I)(t BuNC)4(pyphos)4](Cl)2 (13) and [Mo2Ir2(CH2Cl)(Cl)(t BuNC)4(pyphos)4](Cl)2 (15), respectively, although the corresponding reactions using the Rh(I) analogue 6 did not proceed. Kinetic analysis of the reaction with CH3I suggested that the 1,4-oxidative addition to the Ir(I) complex occurs in an SN2 reaction mechanism.<\/jats:p>","DOI":"10.1021\/ic062474q","type":"journal-article","created":{"date-parts":[[2007,7,3]],"date-time":"2007-07-03T08:00:35Z","timestamp":1183449635000},"page":"6702-6714","source":"Crossref","is-referenced-by-count":22,"title":["Linear Metal\u2212Metal-Bonded Tetranuclear M\u2212Mo\u2212Mo\u2212M Complexes\n(M = Ir and Rh):\u2009 Oxidative Metal\u2212Metal Bond Formation in a\nTetrametallic System and 1,4-Addition Reaction of Alkyl Halides"],"prefix":"10.1021","volume":"46","author":[{"given":"Masato","family":"Ohashi","sequence":"first","affiliation":[{"name":"Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Asuka","family":"Shima","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tobias","family":"R\u00fcffer","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hitoshi","family":"Mizomoto","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yutaka","family":"Kaneda","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kazushi","family":"Mashima","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2007,7,3]]},"reference":[{"key":"2026091506571129600_micit1","unstructured":"Cotton\n              F. 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Am. Chem. Soc.\u00a01984, 106, 5430. (i) LippardS. J.Science\u00a01982, 218, 1075."},{"key":"2026091506571129600_micit13","unstructured":"Examples for rhodium and iridium compounds:\u2009 (a) TejelC.; CirianoM. A.; VillarroyaB. E.; L\u00f3pezJ. A.; LahozF. J.; OroL. A.  Angew. Chem., Int. Ed.\u00a02003, 42, 530. (b) TejelC.; CirianoM. A.; VillarroyaB. E.; GelpiR.; L\u00f3pezJ. A.; LahozF. J.; OroL. A.Angew. Chem., Int. Ed.\u00a02001, 40, 4084. (c) TejelC.; CirianoM. A.; L\u00f3pezJ. A.; LahozF. J.; OroL. A.Angew. Chem., Int. Ed.\u00a01998, 37, 1542. (d) CirianoM. A.; Sebasti\u00e1nS.; OroL. A.; TiripicchioA.; Tiripicchio-CamelliniM.Angew. Chem., Int. Ed.\u00a01988, 27, 402. (e) MannK. R.; DiPierroM. J.; GillT. P.J. Am. Chem. Soc.\u00a01980, 102, 3965."},{"key":"2026091506571129600_micit14","doi-asserted-by":"crossref","unstructured":"Examples for infinite Rh\u2212chain compounds:\u2009 (a) PruchnikF. P.; JakimowiczP.; CiunikZ.; StanislawekK.; OroL. A.; TejelC.; CirianoM. A.  Inorg. Chem. Commun.\u00a02001, 4, 19. (b) PraterM. E.; PenceL. E.; Cl\u00e9racR.; FinnisG. M.; CampanaC.; Auban-SenzierP.; J\u00e9romeD.; CanadellE.; DunbarK. R.J. Am. Chem. Soc.\u00a01999, 121, 8005. (c) FinnisG. M.; CanadellE.; CampanaC.; DunbarK. R.Angew. Chem., Int. Ed.\u00a01996, 35, 2772.10.1016\/S1387-7003(00)00183-0","DOI":"10.1021\/ja991130e"},{"key":"2026091506571129600_elcit17","doi-asserted-by":"publisher","first-page":"726","DOI":"10.1016\/S1387-7003(01)00314-8","volume":"4","author":"Pruchnik","year":"2001","journal-title":"Inorg. Chem. Commun."},{"key":"2026091506571129600_micit15","unstructured":"Examples for linear heterometallic cluster:\u2009 (a) Cl\u00e9racR.; CottonF. A.; DunbarK. R.; MurilloC. A.; WangX.  Inorg. Chem.\u00a02001, 40, 420. (b) CottonF. A.; MurilloC. A.; RoyL. E.; ZhouH.-C.Inorg. Chem.\u00a02000, 39, 1743. (c) BalchA. L.; CatalanoV. J.; NollB. C.; Olmstead. M. M. J. Am. Chem. Soc.\u00a01990, 112, 7558. (d) BalchA. L.; CatalanoV. J.; OlmsteadM. M.J. Am. 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