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RESEARCH ARTICLE
Contents Vol 73(12)

Electronically Induced Steric Clash: Synthesis of NMe2-Modified β-Diketiminate-Supported Boron Difluoride Compounds

Balasubramanian Murugesapandian A , Rakesh Ganguly B , Peter T. K. Lee C , Milena Petković D F , Jason A. C. Clyburne C F and Dragoslav Vidović https://orcid.org/0000-0003-4269-3995 E F
+ Author Affiliations
- Author Affiliations

A Department of Chemistry, Bharathiar University, Coimbatore 641 046, Tamil Nadu, India.

B Department of Chemistry, Shiv Nadar University, NH – 91, Tehsil Dadri, Gautam Buddha Nagar, Uttar Pradesh – 201314, India.

C Atlantic Centre for Green Chemistry, Department of Chemistry, Saint Mary’s University, Halifax, NS B3H 3C3, Canada.

D Faculty of Physical Chemistry, University of Belgrade, Studentski Trg 12-16, 11000 Belgrade, Republic of Serbia.

E School of Chemistry, Monash University, Clayton, Vic. 3800 Australia.

F Corresponding authors: Email: milena@ffh.bg.ac.rs; jason.clyburne@smu.ca; drasko.vidovic@monash.edu

Australian Journal of Chemistry 73(12) 1219-1225 https://doi.org/10.1071/CH20188
Submitted: 8 June 2020  Accepted: 30 July 2020   Published: 21 August 2020

Abstract

We report on the synthesis and structural features of NMe2-modified β-diketiminate-supported boron difluoride compounds (LArBF2: LAr = [HC(NAr)2(CNMe2)2]–; LPh: Ar = Ph; LTol: Ar = p-tolyl; LXyl: Ar = m-xylyl). The title compounds were prepared in moderate yields (~65 %) by in situ deprotonation of the corresponding ligands LArH using KH, followed by the addition of BF3OEt2. According to solid-state and theoretical analyses of the BF2 compounds, the lone pair at each NMe2 group is involved in electron delocalization within the central BC3N2 ring. As a result, the N-aryl substituents sterically clash with the NMe2 groups, causing this central ring to pucker. Several attempts were made to prepare heavy analogues (e.g. LArBX2, X = Cl, Br, I) but only unidentifiable product mixtures were observed. It appears that the observed steric clash between the N-aryl substituents and the NMe2 groups prevented the formation of these heavy analogues.


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