Heteroleptic Magnesium n-Butyl on a Chemically Non-innocent 2-Anilidomethylpyridine Ligand Leading to Diverse Magnesium Hydrides.

Molecular magnesium hydrides and hydride-rich clusters are of significant interest for applications ranging from catalysis and small molecule activation to hydrogen storage. Here, we investigate the 2-anilidomethylpyridine framework NNL as an ancillary support for magnesium organometallics with a special emphasis on hydrides. The proligand NNLH (N-[2,6-bis(1-methylethyl)phenyl]-α,6-diphenyl-2-pyridinemethanamine) gives [(NNL)Mg(nBu)(thf)] (1) by nbutane elimination from Mg(nBu)2(thf)n. A stronger donor such as DMAP replaces the THF from 1 to give [(NNL)Mg(nBu)(dmap)] (2). Both are air-sensitive, and 1 is adventitiously oxidized into [(NNL)Mg(µ-OnBu)]2 (32). The homoleptic [(NNL)2Mg] (8) is made from 1 and a second equiv of NNLH. 1's terminal nBu group is selectively protonated by HN(SiMe3)2 to give [(NNL)MgHMDS] (4; HMDS = N(SiMe3)2), whereas Ph3SiOH partially protonates the backbone anilide as well to give a mixture of [(NNL)Mg(OSiPh3)(thf)] (5) and free NNLH. Like HN(SiMe3)2, aprotic MeOTf also reacts by selectively abstracting the nBu group from 1 to give [(NNL)Mg(µ:κ2-O,O'-OTf)(thf)]2 (62). Interestingly, screening the common synthetic routes for magnesium hydrides leads to diverse outcomes upon varying the Mg precursors and hydride sources. 1 and PhSiH3 give the hydride cluster [{(NNL)2Mg2(µ-H)}2(µ-H)4Mg] (7), whereas 2 and PhSiH3 give the molecular complex [(NNLde)Mg(dmap)2] (9) with a dearomatized pyridyl backbone. 1 and HBpin (pinacolborane) give a product mixture, from which a different hydride cluster [(NNL)2Mg2(µ-H)}2(µ:κ2-O,O'-O2C2Me4)] (10) is identified, showing a rare instance of complete deborylation of a HBpin molecule. 1 and HBcat (catecholborane) also give a product mixture, one of which is the borylated ligand [(NNL)Bcat] (11). HBpin with 4 as the Mg precursor takes the ligand borylation route more selectively to give [(NNL)Bpin] (12). Last, 1 reacts with iPrNH2BH3 to give [(NNL)Mg{NH(iPr)BH3}] (13), which shows a slow and fractional conversion into the dinuclear mixed hydrido amidoborane [(NNL)2Mg2(µ-H){(µ-NH(iPr)BH3}] (14) by partial ß-hydride elimination. In comparison, [(NNL)Mg(iPrNHBH3)(dmap)] (15) arising from the DMAP-bound 2 and iPrNH2BH3 is stable toward such elimination.

2-Anilidomethylpyridine-Derived Three-Coordinate Zinc Hydride: The Journey Unveils Anilide Backbone's Reactive Nature.

Low-coordinate heteroleptic zinc hydrides are catalytically important but rare and synthetically challenging. We herein report three-coordinate monomeric zinc hydride on a 2-anilidomethylpyridine framework (NNL). The synthetic success comes through systematically screening a few different routes from different precursors. During the process, the ligand's anilide backbone interestingly appears to be more reactive than Zn's terminal site to electrophilic Lewis and Brønsted acids. The proligand NNLH reacts with [Zn{N(SiMe3)2}2] and ZnEt2 to give [(NNL)ZnA] (A = N(SiMe3)2 (1), Et(2)). Both are inert to PhSiH3 and H2 but react with HBpin only through the internal Zn-Nanilide bond to give the borylated ligand NNLBpin (3). The reactions of 1 and 2 with Ph3EOH (E = C, Si) afford a series of divergent compounds like [(NNLH)Zn(OSiPh3)2] (4), [Zn3(OSiPh3)4Et2] (5), and [EtZn(OCPh3)] (6). But in all cases, it is invariably the Zn-Nanilide bond protonated by the -OH with equal or higher preference than the terminal Zn-N or Zn-C bonds. A DFT analysis rationalizes the origin of such a reactivity pattern. Realizing that an acid-free route might be the key, reacting [(NNL)Li] with ZnBr2 gives [(NNL)Zn(µ-Br)]2 (7), which on successively treating with KOSiPh3 and PhSiH3 gives the desired [(NNL)ZnH] (8) as a three-coordinate monomer with a terminal Zn-H bond. Estimating the ligand steric in 8 shows the openness in Zn's coordination sphere, a desired criterion for efficient catalysis. This and a positive influence of the pyridyl sidearm is reflected in 8's superior activity in hydroborating PhC(O)Me by HBpin in comparison to Jones' two-coordinate anilido zinc hydride.

A 2-Anilidomethylpyridine Ligand Framework Showcasing Hydride Storage and Transfer Abilities in Its Aluminum Chemistry.

Dearomatized 1,4-dihydropyridyl motifs are significant in both chemistry and biology for their potential abilities to deliver the stored hydride, driven by rearomatization. Biological cofactors like nicotinamide adenine dinucleotide (NADH) and organic 'hydride sources' like Hantzsch esters are prime examples. An organoaluminum chemistry on a 2-anilidomethylpyridine framework is reported, where such hydride storage and transfer abilities are displayed by the ligand's pyridyl unit. The pyridylmethylaniline proligand (NN LH) is simultaneously deprotonated and 1,4-hydroaluminated by AlH3 (NMe2 Et) to [(NN Lde )AlH(NMe2 Et)] (1; NN Lde =hydride-inserted dearomatized version of NN L). A hydride abstraction by B(C6 F5 )3 rearomatizes the pyridyl moiety to give the cationic aluminum hydride [(NN L)AlH(NMe2 Et)][HB(C6 F5 )3 ] (6). Notably, such chemical non-innocence is priorly unseen in this established ligand class. The hydroalumination mechanism is investigated by isolating the intermediate [(NN L)AlH2 ] (2) and by control experiments, and is also analyzed by DFT calculation. The results advocate an intriguing 'self-promoting' pathway, which underlines alane's Lewis acid/Brønsted base duality. NMe2 Et carrying the alane also plays a crucial role. In contrast, the chemistry between NN LH and AlMe3 is much different, giving only [(NN L)AlMe2 ] (4) from the adduct [(NN LH)AlMe3 ] (3) by deprotonation but not a subsequent pyridyl dearomatization in the presence or absence of NMe2 Et. This divergence is also justified by DFT analyses.

Fluorenyl-tethered N-heterocyclic carbene (NHC): an exclusive C-donor ligand for heteroleptic calcium and strontium chemistry.

Exclusive C-donating ligands are rarely used with kinetically labile heavier alkaline earths (Ca, Sr, Ba). We report herein the aptitude of a combination of NHC with fluorenyl connected by a flexible -(CH2)2- linker as a ligand support for heteroleptic Ca- and Sr-N(SiMe3)2 and iodides. The Ca-N(SiMe3)2 complex even catalyzes the intramolecular hydroamination of aminoalkenes to showcase the effectiveness of this ligand framework.

Cyclopentadienyl Complexes of the Alkaline Earths in Light of the Periodic Trends.

The electron-rich cyclopentadienyl and the analogous indenyl and fluorenyl ligands (collectively denoted here as Cp') have been impactful in stabilizing electron-deficient metal centers including the highly electropositive alkaline earths. Being in the s-block, the group 2 metals follow a major periodic variation in their atomic and ionic properties which is reflected in those Cp' compounds. This article presents an overview of this class of compounds for all the five metals from beryllium to barium (radium is excluded for its radioactivity), highlighting their systematic variation.