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Ten-vertex Metalloborane Chemistry. Aspects of the Iridadecaborane closo->isonido->isocloso Structural Continuum

DOI: 10.1039/DT9920000563

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 563 - 576 (1992)

Update date:2022-09-26

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Authors:

Bould, JonathanBould, Jonathan

Kennedy, John D.Kennedy, John D.

Thornton-Pett, MarkThornton-Pett, Mark

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Article abstract of DOI:10.1039/DT9920000563

Reaction of the arachno-(1-) or nido-(1-) anions with at ca. 298 K gives, in addition to previously reported species, pale violett <7,7,9-(PPh3)3-isonido-7-IrB9H10> 2 in yields of ca. 2percent.Single crystal X-ray diffraction analysis and multinuclear NMR spectroscopy reveal a ten-vertex cluster of an 'isonido' type that is based upon the closo eleven-vertex structure of (2-) from which a four-connected vertex is removed to generate a four-membered open face.There are two fluxional bridging hydrogen atoms associated with the open face.Thermolysis at ca. 355 K of solutions in 1,1,2,2-tetrachloroethane of yellow 4 result in loss of hydrogen and the formation of deep purple 5 (0-5 percent) and royal blue 6 (0-5 percent).Single crystal X-ray diffraction shows that compounds 5 and 6 also have isonido cluster structures, although 5 does not have bridging hydrogen atoms on the open face, suggesting that any extra electrons required for it to be isoelectronic with 2 and 6 may originate from the metal vertex.The structure of the crystal of compound 6 examined was found to contain ca. 25 mole percent of the isostructural 3-chloro derivative 6a.The ten-vertex clusters 2,5 and 6 are part of a structural continuum ranging from closo through isonido to isocloso.It is proposed that these isonido compounds represent intermediates in a variety of reactions involving nido to isocloso cluster oxidations and nido to nido rearrangements.

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Product name:{3-Cl-7,9-(PPh3)2-7-(o-Ph2PC6H4)-isonido-7-IrB9H-10}

Cas No:140693-33-0

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