Abstract
This chapter provides a comprehensive review of M→Z complexes, that is to say complexes featuring Lewis acids coordinated as σ-acceptor ligands. The preparation, structure and bonding, as well as the characteristic features of M→Z complexes are discussed. Only Lewis acids derived from the p-block elements are considered, with a focus on two-center M→Z interactions supported by donor sidearms. The chapter is organized according to (1) the nature of the Lewis acid moiety (based on group 13, 14, 15 or 16 elements), (2) the way the M→Z interaction is formed (by B–H activation of pro-ligands or direct coordination of preformed ambiphilic ligands) and (3) the type of complexes (M→Z interactions supported by 3, 2 or 1 donor sidearms, unsupported M→Z interactions).
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- 1.
- 2.
- 3.
A S-bridged dinuclear Pd complex is formed before addition of PMe3.
- 4.
The 5-mercapto-1,2,4-triazolyl sidearm may coordinate through the N atom in β position to B, but only S-coordination was observed.
- 5.
For a review on BCn multicenter coordination to TM, see [19].
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- 7.
The geometry around P in phosphenium complexes can be trigonal planar or pyramidal. Planar phosphenium complexes feature MP bonds with double-bond character and can be assimilated to Fischer/Schrock-type carbene complexes. Pyramidal phosphenium complexes feature single MP bonds with a stereochemical active lone pair at P. Their bonding situation can correspond to phosphenium Z-type complexes or phosphido complexes without π(P→M) donation. The difference between the two resides in the nature of the σ interaction/bond between P and M.
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Bouhadir, G., Bourissou, D. (2016). Coordination of Lewis Acids to Transition Metals: Z-Type Ligands. In: Mingos, D. (eds) The Chemical Bond III. Structure and Bonding, vol 171. Springer, Cham. https://doi.org/10.1007/430_2015_201
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