Please use this identifier to cite or link to this item: https://hdl.handle.net/10356/99344
Title: (Dimethylamino) borylene and related complexes of electron-rich metal fragments : generation of nucleophile-resistant cations by spontaneous halide ejection
Authors: Addy, David A.
Pierce, Glesni A.
Jemmis, Eluvathingal D.
Phillips, Nicholas
Vidović, Dragoslav
Krämer, Tobias
Mallick, Dibyendu
Reid, Gill
Aldridge, Simon
Keywords: DRNTU::Science::Physics
Issue Date: 2012
Source: Addy, 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.
Series/Report no.: Organometallics
Abstract: Spontaneous 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.
URI: https://hdl.handle.net/10356/99344
http://hdl.handle.net/10220/13713
DOI: 10.1021/om201144e
Fulltext Permission: none
Fulltext Availability: No Fulltext
Appears in Collections:SPMS Journal Articles

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