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A Bismuth–Arene σ‐Complex – On the Edge of Menshutkin‐Type Complexes
Author(s) -
Bresien Jonas,
Schulz Axel,
Thomas Max,
Villinger Alexander
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201900003
Subject(s) - chemistry , bismuth , halogen , reactivity (psychology) , chloride , medicinal chemistry , azide , cycloaddition , covalent bond , decomposition , stereochemistry , lewis acids and bases , organic chemistry , catalysis , alkyl , medicine , alternative medicine , pathology
Mes*N(SiMe 3 )BiCl 2 ( 1 , Mes* = 2,4,6‐tri‐ tert ‐butylphenyl) can be referred to as a hidden iminobismuthane, Mes*N=BiCl, which was thought to be generated in‐situ upon Me 3 SiCl elimination triggered by a Lewis acid such as GaCl 3 . Therefore, the reactivity of aminobismuthane 1 was studied to find a synthesis route for the formation of a tetrazabismuthole in a [3+2] cycloaddition reaction with a covalently bound azide. However, reaction of 1 with GaCl 3 cleanly led to [Mes*N(SiMe 3 )BiCl][GaCl 4 ] ( 2 [GaCl 4 ]), a compound with a Bi‐arene σ‐complex. Utilizing Ag[WCA] salts (WCA = weakly coordinating anion) for chloride abstraction, a C–C coupling product ( 3 ) was identified. The diiodide species Mes*N(SiMe 3 )BiI 2 ( 4 ) as precursor for a diazido species and the azido‐chloride compound Mes*N(SiMe 3 )Bi(N 3 )Cl ( 5 ) were also prepared to explore the possibility of a BiN 4 heterocycle formation, again upon Me 3 SiX elimination (X = halogen, N 3 ), but 4 and 5 were unstable towards decomposition into a black precipitate and a complex product mixture. The structure and bonding of all isolated bismuth species is discussed.