Projects per year
Abstract
Density functional theory (DFT) calculations demonstrate that the previously reported reaction of [(BDI)Mgn-Bu] (BDI = HC{(Me)CN-Dipp}2; Dipp – 2,6-di-iso-propylphenyl) with the silaborane, Me2PhSi-Bpin, provides the magnesium silanide derivative, [(BDI)MgSiMe2Ph], through the intermediacy of a short lived silyl-pinacolato-organoborate species. The nucleophilic character of the resultant silanide anion is assayed through a series of reactions with RN=C=NR (R = i-Pr, Cy, t-Bu) and p-tolN=C=Np-tol. When performed in a strict 1:1 stoichiometry, all four reactions result in silyl addition to the carbodiimide carbon center and formation of the corresponding beta-diketiminato magnesium sila-amidinate complexes. Although performance of the reaction of [(BDI)MgSiMe2Ph] with two equivalents of p-tolylcarbodiimide also results in the formation of a sila-amidinate anion, the second equivalent is observed to engage with the nucleophilic gamma-methine carbon of the BDI ligand to provide a tripodal di-imino-iminoamidate ligand. This behaviour is judged to be a consequence of the enhanced electrophilicity of the N-aryl substituted carbodiimide reagent, a viewpoint supported by a further reaction with the N-isopropyl sila-amidinate complex, [(BDI)Mg(i-PrN)2CSiMe2Ph]. This latter reaction not only provides an identical di-imino-iminoamidate ligand but also results in twofold insertion of p-tolN=C=Np-tol into a Mg-N bond between the magnesium center and the sila-amidinate anion.
Original language | English |
---|---|
Pages (from-to) | 13679–13689 |
Number of pages | 11 |
Journal | Inorganic Chemistry |
Volume | 59 |
Issue number | 18 |
Early online date | 4 Sept 2020 |
DOIs | |
Publication status | Published - 21 Sept 2020 |
Fingerprint
Dive into the research topics of 'Nucleophilic Magnesium Silanide and Silaamidinate Derivatives'. Together they form a unique fingerprint.Projects
- 2 Finished
-
Nucleophilic alkaline earth boryls: from conception and theory to application
Hill, M. (PI), Cresswell, A. (CoI) & McMullin, C. (Researcher)
Engineering and Physical Sciences Research Council
1/05/18 → 31/07/22
Project: Research council
-
Augmentation of Alkaline Earth Reactivity: An FLP Analogy
Hill, M. (PI)
Engineering and Physical Sciences Research Council
8/02/16 → 6/02/20
Project: Research council
Equipment
-
Avance 300 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (1South)
Material and Chemical Characterisation (MC2)Facility/equipment: Equipment
-
Balena High Performance Computing (HPC) System
Facility/equipment: Equipment
-
Propulse 500 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (1South)
Material and Chemical Characterisation (MC2)Facility/equipment: Equipment