Ghosh, Sundargopal ; Noll, Bruce C. ; Fehlner, Thomas P. (2008) Expansion of iridaborane clusters by addition of monoborane. Novel metallaboranes and mechanistic detail Dalton Transactions (3). pp. 371-378. ISSN 1477-9226
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Official URL: http://pubs.rsc.org/en/content/articlelanding/2008...
Related URL: http://dx.doi.org/10.1039/B715040G
Abstract
This work reports the results of a thermally driven cluster expansion of arachno-1-{η5-C5Me5IrH2}B3H7, 1, with BH3·THF. In addition to the previously reported product, arachno-1-{ η5-C5Me5IrH}B4H9, 2, formed at lower temperatures, reaction at 100 °C permits the isolation of four new iridaboranes. Two products, nido-1-(η5-C5Me5Ir)B5H9, 3, and nido-3-(η5-C5Me5Ir)B9H13, 4, contain a single Ir atom and five and nine framework boron atoms, respectively. One, nido-3,4-(η5-C5Me5Ir)2B8H12, 5, contains two Ir atoms and eight framework boron atoms. Their structures are predicted by the electron counting rules to be a nido-iridahexaborane, 3, nido-iridadecaborane, 4, and nido-diiridadecaborane, 5. The accuracy of these predictions in each case is established experimentally by spectroscopic characterization in solution and structure determinations in the solid state. A less stable metallaborane has been identified and the available spectroscopic and crystallographic information are consistent with the formulation nido-3,4-(η5-C5Me5Ir)2B8H13 (µ-BH2), 6, i.e., a species containing an exopolyhedral bridging BH group. These new observations, along with earlier ones on ruthenaborane cluster systems, are used to fully define a general mechanism for a cluster expansion reaction, i.e., addition of borane to form an exopolyhedral adduct followed by cage insertion.
Item Type: | Article |
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Source: | Copyright of this article belongs to Royal Society of Chemistry. |
ID Code: | 110816 |
Deposited On: | 31 Jan 2018 12:31 |
Last Modified: | 31 Jan 2018 12:31 |
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