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H3B·NMe3 σ-complexes of d8 [(L1)Rh][BArF4] and d10 [(L1)Ag][BArF4] (where L1 = 2,6-bis-[1-(2,6-diisopropylphenylimino)ethyl]pyridine) have been prepared and structurally characterised. Analysis of the molecular and electronic structures reveal important but subtle differences in the nature of the bonding in these σ-complexes, which differ only by the identity of the metal centre and the d-electron count. With Rh the amine-borane binds in an η2:η2 fashion, whereas at Ag the unsymmetrical {AgH3B·NMe3} unit suggests a structure lying between the η2:η2 and η1 extremes.

dalton transactions

A d10 Ag(<scp>i</scp>) amine–borane σ-complex and comparison with a d8 Rh(<scp>i</scp>) analogue: structures on the η1 to η2:η2 continuum

A d10 Ag(i) amine–borane σ-complex and comparison with a d8 Rh(i) analogue: structures on the η1 to η2:η2 continuum

A d¹⁰ Ag(i) amine–borane σ-complex and comparison with a d⁸ Rh(i) analogue: structures on the η¹ to η²:η² continuum