dc.contributor.authorAddy, David A.
dc.contributor.authorPhillips, Nicholas
dc.contributor.authorPierce, Glesni A.
dc.contributor.authorVidović, Dragoslav
dc.contributor.authorKrämer, Tobias
dc.contributor.authorMallick, Dibyendu
dc.contributor.authorJemmis, Eluvathingal D.
dc.contributor.authorReid, Gill
dc.contributor.authorAldridge, Simon
dc.date.accessioned2013-09-30T03:09:22Z
dc.date.available2013-09-30T03:09:22Z
dc.date.copyright2012en_US
dc.date.issued2012
dc.identifier.citationAddy, D. A., Phillips, N., Pierce, G. A., Vidović, D., Krämer, T., Mallick, D., et al. (2012). (Dimethylamino) borylene and related complexes of electron-rich metal fragments : generation of nucleophile-resistant cations by spontaneous halide ejection. Organometallics, 31(3), 1092–1102.
dc.identifier.urihttp://hdl.handle.net/10220/13713
dc.description.abstractSpontaneous halide ejection from a three-coordinate Lewis acid has been shown to offer a remarkable new route to cationic metal complexes featuring a linear, multiply bonded boron-donor ligand. The exploitation of electron-rich [CpM(PR3)2] fragments within boryl systems of the type LnMB(hal)NR2 leads to the spontaneous formation in polar solvents of chemically robust borylene complexes, [LnM(BNR2)]+, with exceptionally low electrophilicity and short M–B bonds. This is reflected by M–B distances (ca. 1.80 Å for FeB systems) which are more akin to alkyl-/aryl-substituted borylene complexes and, perhaps most strikingly, by the very low exothermicity associated with the binding of pyridine to the two-coordinate boron center (ΔH = −7.4 kcal mol–1, cf. −40.7 kcal mol–1 for BCl3). Despite the strong π electron release from the metal fragment implied by this suppressed reactivity and by such short M–B bonds, the barrier to rotation about the Fe═B bond in the unsymmetrical variant [CpFe(dmpe)(BN{C6H4OMe-4}Me)]+ is found to be very small (ca. 2.9 kcal mol–1). This apparent contradiction is rationalized by the orthogonal orientations of the HOMO and HOMO-2 orbitals of the [CpML2]+ fragment, which mean that the M–B π interaction does not fall to zero even in the highest energy conformation.en_US
dc.language.isoenen_US
dc.relation.ispartofseriesOrganometallicsen_US
dc.subjectDRNTU::Science::Physics
dc.title(Dimethylamino) borylene and related complexes of electron-rich metal fragments : generation of nucleophile-resistant cations by spontaneous halide ejectionen_US
dc.typeJournal Article
dc.contributor.schoolSchool of Physical and Mathematical Sciencesen_US
dc.identifier.doihttp://dx.doi.org/10.1021/om201144e


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