1373393-16-8Relevant articles and documents
Mono-and Bimetallic Aluminum Alkyl, Alkoxide, Halide and Hydride Complexes of a Bulky Conjugated Bis-Guanidinate(CBG) Ligand and Aluminum Alkyls as Precatalysts for Carbonyl Hydroboration
Peddarao, Thota,Sarkar, Nabin,Nembenna, Sharanappa
, p. 4693 - 4702 (2020)
Tetra-aryl-substituted symmetrical conjugated bis-guanidine (CBG) ligands such as L1-3 (3H) [L(3H) = {(ArHN)(ArHN)C=N-C=NAr(NHAr)}; Ar = 2,6-Me2-C6H3 (L1(3H)), 2,6-Et2-C6H3 (L2(3H)), and 2,6-iPr2-C6H3 (L3(3H))] have been employed to synthesize a series of four-and six-membered aluminum heterocycles (1-8) for the first time. Generally, aluminum complexes bearing N,N′-chelated guanidinate and β-diketiminate/dipyrromethene ligand systems form four-and six-membered heterocycles, respectively. However, the conjugated bis-guanidine ligand has the capability of forming both four-and six-membered heterocycles possessing multimetal centers within the same molecule; this is due to the presence of three acidic protons, which can be easily deprotonated (at least two protons) upon treatment with metal reagents. Both mono-and dinuclear aluminum alkyls and mononuclear aluminum alkoxide, halide, and hydride complexes have been structurally characterized. Further, we have demonstrated the potential of mononuclear, six-membered CBG aluminum dialkyls in catalytic hydroboration of a broad range of aldehydes and ketones with pinacolborane (HBpin).
Reactivity of a Molecular Magnesium Hydride Featuring a Terminal Magnesium-Hydrogen Bond
Schnitzler, Silvia,Spaniol, Thomas P.,Okuda, Jun
, p. 12997 - 13006 (2016)
The reactivity of the molecular magnesium hydride [Mg(Me3TACD·AliBu3)H] (1) featuring a terminal magnesium-hydrogen bond and an NNNN-type macrocyclic ligand, Me3TACD ((Me3TACD)H = Me3[12]aneN4 = 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane), can be grouped into protonolysis, oxidation, hydrometalation, (insertion), and hydride abstraction. Protonolysis of 1 with weak Br?nsted acids HX such as terminal acetylenes, amines, silanols, and silanes gave the corresponding derivatives [Mg(Me3TACD·AliBu3)X] (X = C=CPh, 3; HN(3,5-Me2-C6H3), 4; OSiMe3, 5; OSiPh3, 6; Cl, 7; Br, 8). Single-crystal X-ray diffraction of anilide 4 showed a square-pyramidal coordination geometry for magnesium. No correlation with the pKa values of the acids was detected. Oxidation of 1 with elemental iodine gave the iodide [Mg(Me3TACD·AliBu3)I] (9), and oxidation with nitrous oxide afforded the μ-oxo-bridged compound [{Mg(Me3TACD·AliBu3)}2(μ-O)] (10) with a linear Mg-O-Mg core, as characterized by single-crystal X-ray diffraction. The Mg-H bond reacted with benzaldehyde, benzophenone, fluorenone, and CO2 under insertion but not with the olefins 1,1,2-triphenylethylene, tert-butylethylene, and cyclopentene. The unstable formate, prepared also by salt metathesis of iodide 9 with potassium formate, revealed ?°O,?°O′ coordination in the solid state. Hydride abstraction with triphenylborane gave the ion pair [Mg(Me3TACD·AliBu3)(thf)][HBPh3] (16), which catalyzed the hydroboration of polar substrates by pinacolborane.
Accessing zinc monohydride cations through coordinative interactions
Lummis, Paul A.,Momeni, Mohammad R.,Lui, Melanie W.,McDonald, Robert,Ferguson, Michael J.,Miskolzie, Mark,Brown, Alex,Rivard, Eric
, p. 9347 - 9351,5 (2014)
We present isolable examples of formal zinc hydride cations supported by N-heterocyclic carbene (NHC) donors, and investigate the dual electrophilic and nucleophilic (hydridic) character of the encapsulated [ZnH]+ units by computational methods
Progressing the Frustrated Lewis Pair Abilities of N-Heterocyclic Carbene/GaR3Combinations for Catalytic Hydroboration of Aldehydes and Ketones
Bole, Leonie J.,Uzelac, Marina,Hernán-Gómez, Alberto,Kennedy, Alan R.,O'Hara, Charles T.,Hevia, Eva
supporting information, p. 13784 - 13796 (2021/07/26)
Exploiting the steric incompatibility of the tris(alkyl)gallium GaR3 (R = CH2SiMe3) and the bulky N-heterocyclic carbene (NHC) 1,3-bis(tert-butyl)imidazol-2-ylidene (ItBu), here we report the B-H bond activation of pinacolborane (HBPin), which has led to
Expedient Hydrofunctionalisation of Carbonyls and Imines Initiated by Phosphacyclohexadienyl Anions
Margeson, Matthew J.,Seeberger, Felix,Kelly, John A.,Leitl, Julia,Coburger, Peter,Szlosek, Robert,Müller, Christian,Wolf, Robert
, p. 3761 - 3764 (2021/06/25)
The ability of phosphacyclohexadienyl anions [Li(1-R-PC5Ph3H2)] [R=Me (1 a), nBu (1 b), tBu (1 c), Ph (1 d) and CH2SiMe3 (1 e)] to initiate hydrofunctionalisation reactions was investigated and compar
