ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
