Alkyl backbone variations in common β-diketiminate ligands and applications to N-heterocyclic silylene chemistry
Abstract
We report the extension of the common β-diketimine proligand class, RArnacnacH (HC(RCNAr)2H), where R is an alkyl group such as Et or iPr, plus Ph, and Ar is a sterically demanding aryl substituent such as Dip = 2,6-diispropylphenyl, Dep = 2,6-diethylphenyl, Mes = 2,4,6-trimethylphenyl or mesityl, Xyl = 2,6-dimethylphenyl, via one-pot condensation procedures. When a condensation reaction is carried out using the chemical dehydrating agent PPSE (polyphosphoric acid trimethylsilylester), β-diketiminate phosphorus(V) products such as (iPrMesnacnac)PO2 can also be obtained, which can be converted to the respective proligand iPrMesnacnacH via alkaline hydrolysis. The RArnacnacH proligands can be converted to their alkali metal complexes with common methods and we have found that deprotonation of iPrDipnacnacH is significantly more sluggish than of related β-diketimines with smaller backbone alkyl groups. The basicity of the RArnacnac- anions can play a role in the success of their salt metathesis chemistry and we have prepared and structurally characterised the EtDipnacnac-derived silicon(II) compounds (EtDipnacnac)SiBr and (EtDipnacnac’)Si, where EtDipnacnac’ is the deprotonated variant MeCHC(NDip)CHC(NDip)Et.
Citation
Bourne , C , Dong , H , McKain , K , Mayer , L C , McKay , A , Cordes , D B , Slawin , A M Z & Stasch , A 2024 , ' Alkyl backbone variations in common β-diketiminate ligands and applications to N-heterocyclic silylene chemistry ' , Dalton Transactions , vol. 53 , no. 23 , pp. 9887-9895 . https://doi.org/10.1039/D4DT01298D
Publication
Dalton Transactions
Status
Peer reviewed
ISSN
1477-9226Type
Journal article
Collections
Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.