Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides

Abstract

Pendent borane Lewis acids provide an avenue for changing a ligand's field strength through acid/base interactions; this strategy was highlighted within a series of biologically-relevant high spin iron hydrides.

Lewis Acid Effects on Calculated Ligand Electronic Parameters

“…We previously observed that such Lewis acid-induced changes can be used to impart comparable ligand electronic effects (−H − , −OR − , −SR − , etc.) within a series of ligands that otherwise exhibit disparate donor properties …”

“…within a series of ligands that otherwise exhibit disparate donor properties. 33 Although controlling the extent of Lewis-acid induced electronic perturbation can facilitate stabilization or promote new divergent reactivity, most reported systems are largely arrived at ad hoc or by using the highly Lewis acidic and commercially available reagent B(C 6 F 5 ) 3 . 34 Despite the ramifications on many reactions, systematic investigations of Lewis acid interaction effects (>3 LAs) to metal-bound substrates are uncommon.…”

A guide to secondary coordination sphere editing

“…98,99 species that exhibited two s-B-H-[Fe] interactions (Scheme 37). 100 In the presence of protic reagents, H-E (E = NH 2 , NHMe, NHPh, OH, PHPh, SPh), H 2 release was noted to give new B-E-[Fe] (E = element) bonds.…”

Palladium–Borane Cooperation: Evidence for an Anionic Pathway and Its Application to Catalytic Hydro‐/Deutero‐dechlorination

“…Thecomplex adopts aseparate ion pair structure.The additional hydrogen atom (which was located in the difference Fourier map and refined isotropically) bridges the Ba nd Pd centers (B-H, 1.21(4) and Pd-H, 1.889(X) ). [19,20] Theboron center is in atetrahedral environment (the sum of the three C-B-C bond angles is reduced to 335.3(5)8 8), while the Pd center adopts ar are trigonal-pyramidal geometry (S(P-Pd-P) = 358.3(7)8 8) with the hydride in the apical position. To our knowledge,this is the first monomeric anionic Pd 0 complex to be structurally characterized.…”