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Issue 47, 2006
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Encapsulation of hydride by molecular main group metal clusters: manipulating the source and coordination sphere of the interstitial ion

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Abstract

The sequential treatment of Lewis acids with N,N′-bidentate ligands and thereafter with ButLi has afforded a series of hydride-encapsulating alkali metal polyhedra. While the use of Me3Al in conjunction with Ph(2-C5H4N)NH gives Ph(2-C5H4N)NAlMe21 and this reacts with MeLi in thf to yield the simple ’ate complex Ph(2-C5H4N)NAlMe3Li·thf 3, the employment of an organolithium substrate capable of β-hydride elimination redirects the reaction significantly. Whereas the use of ButLi has previously yielded a main group interstitial hydride in which H exhibits µ6-coordination, it is shown here that variability in the coordination sphere of the encapsulated hydride may be induced by manipulation of the organic ligand. Reaction of (c-C6H11)(2-C5H4N)NH with Me3Al/ButLi yields [{(c-C6H11)(2-C5H4N)N}6HLi8]+[(But2AlMe2)2Li]6, which is best viewed as incorporating only linear di-coordination of the hydride ion. The guanidine 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hppH) in conjunction with Me2Zn/ButLi yields the µ8-hydride [(hpp)6HLi8]+[But3Zn]·0.5PhMe 7. Formation of the µ8-hydride [(hpp)6HLi8]+[ButBEt3]8 is revealed by employment of the system Et3B/ButLi. A new and potentially versatile route to interstitial hydrides of this class is revealed by synthesis of the mixed borohydride–lithium hydride species [(hpp)6HLi8]+[Et3BH]10 and [(hpp)6HLi8]+[(Et3B)2H]12 through the direct combination of hppLi with Et3BHLi.

Graphical abstract: Encapsulation of hydride by molecular main group metal clusters: manipulating the source and coordination sphere of the interstitial ion

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Publication details

The article was received on 04 Sep 2006, accepted on 29 Sep 2006 and first published on 18 Oct 2006


Article type: Paper
DOI: 10.1039/B612782G
Citation: Dalton Trans., 2006, 5574-5582
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    Encapsulation of hydride by molecular main group metal clusters: manipulating the source and coordination sphere of the interstitial ion

    S. R. Boss, M. P. Coles, V. Eyre-Brook, F. García, R. Haigh, P. B. Hitchcock, M. McPartlin, J. V. Morey, H. Naka, P. R. Raithby, H. A. Sparkes, C. W. Tate and A. E. H. Wheatley, Dalton Trans., 2006, 5574
    DOI: 10.1039/B612782G

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