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Benzynechromium tricarbonyl. Further synthetic studies

TitleBenzynechromium tricarbonyl. Further synthetic studies
Publication TypeJournal Article
Year of Publication1996
AuthorsCullen, WR, Rettig, SJ, Zhang, HL
JournalInorganica Chimica Acta
Date PublishedOct
Type of ArticleArticle
ISBN Number0020-1693
Keywords(BENZYNE)CHROMIUM TRICARBONYL, BENZYNE, carbonyl complexes, CHROMIUM COMPLEXES, cluster complexes, CLUSTERS, COMPLEXES, crystal structures, CRYSTAL-STRUCTURES, MOLECULAR-STRUCTURES, OSMIUM, osmium complexes, ruthenium complexes

{The thermolysis of Ru-3(CO)(11)[Ph(2)PC(6)H(5)Cr(CO)(3)] affords two isomers of the benzyne derivative Ru-3(CO)(7)(C6H4)[PPhC(6)H(5)Cr(CO)(3)](2) ((5) and (6)). The crystal structure of 5, previously determined, shows the phenyl groups are trans to the Ru-3-triangle; in 6 they are probably cis and on the same side of the Ru-3-triangle as the benzyne moiety. Os-3(CO)(11)[Ph(2)PC(6)H(5)Cr(CO)(3)] decomposes on heating to afford a benzyne derivative of a less common class Os-3(CO)(9)(C6H4)[PC6H5Cr(CO)(3)] (7), and an electron deficient molecule Os-3(CO)(8)(PhPC(6)H(4))[Ph(2)PC(6)H(5)Cr(CO)(3)] (8), in which the PhPC(6)H(4) moiety acts as a four-electron donor. The isopropylphosphine derivatives M(3)(CO)(11)[(Pr2PC6H5Cr)-P-i(CO)(3)] (M=Ru, Os), also undergo thermolysis to afford HRu3(CO)(8)[C6H4Cr(CO)(3)](PPr2i) (10), Ru(CO)(3)[(Pr2PC6H5Cr)-P-i(CO)(3)](2) (11), H2Os3(CO)(8)[(PrPC6H4Cr)-P-i(CO)(3)] (12) and H2Os3(CO)(8)[(PrPC6H4Cr)-P-i(CO)(3)][(Pr2PC6H5Cr)-P-i(CO)(3)] (13). Complex 10 is probably a benzynechromium tricarbonyl derivative with a Cr-Ru bond. The phosphines are trans in complex 11, a derivative of Ru(CO)(5). The structures of complexes 12 and 13 are closely related and the orthometalated [PC6H4Cr(CO)(3)] moiety is acting as a four-electron donor to the cluster. Crystal data: for 8 (C41H24CrO11Os3P2 . CH2Cl2): monoclinic

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