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Mixed amide thiolate complexes of zinc with low coordination number at the metal atom
Author(s) -
Grützmacher Hansjörg,
Steiner Matthias,
Pritzkow Hans,
Zsolnai Laszlo,
Huttner Gottfried,
Sebald Angelika
Publication year - 1992
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19921251006
Subject(s) - chemistry , amide , zinc , dimer , toluene , metal , medicinal chemistry , crystal structure , stereochemistry , yield (engineering) , crystallography , organic chemistry , materials science , metallurgy
Three different thiophenoles 2,4,6‐(CF 3 ) 3 C 6 H 2 SH ( 4 ), 2,4,6‐( i Pr) 3 C 6 H 2 SH ( 5 ), and 2,6‐(Me 3 Si) 2 C 6 H 3 SH ( 6 ) with bulky sub‐stituents in ortho position were treated with Zn[N(SiMe 3 ) 2 ] 2 ( 7 ) in a non‐coordinating solvent like CH 2 Cl 2 or toluene to yield mixed amide thiolate zinc complexes Zn 2 [N(SiMe 3 ) 2 ]{S[2,4,6‐(CF) 3 C 6 H 2 ]} 3 ( 8 ), Zn 3 [N(SiMe 3 ) 2 ] 2 {S[2,4,6‐( i Pr) 3 C 6 H 2 ]} 4 ( 9 ), and Zn 2 {S[2,6‐(Me 3 Si) 2 C 6 H 3 ]} 4 ( 10 ), respectively. These compounds comprise low‐coordinated zinc atoms. Initially, the reactions were performed in a 1:1 ratio of the reactants. However, in no reaction the expected {Zn[N(SiMe 3 ) 2 ](SR)} x (X = 1,2,3…) species were obtained but compounds which are richer in thiolate substituents (SR/NR 2 > 1) even if a large excess of amide 7 was used. Distinct from these, the reaction between 7 and 2,6‐( i Pr) 2 C 6 H 3 OH ( 14 ) in a 1:1 ratio afforded indeed dimer Zn 2 [N(SiMe 3 ) 2 ] 2 {O[2,6‐( i Pr) 2 C 6 H 3 ]} 2 ( 15 ). The molecular structures of 8, 9, 10 , and 15 in the crystal are elucidated by X‐ray structural analyses and compared with proposed structures in solution based on multinuclear NMR experiments.