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The Insertion of Heterocumulenes into Zn−H and Zn−OH Bonds of Pyrazolylborate−Zinc Complexes
Author(s) -
Rombach Michael,
Brombacher Horst,
Vahrenkamp Heinrich
Publication year - 2002
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 - 10.1002/1099-0682(20021)2002:1<153::aid-ejic153>3.0.co;2-k
Subject(s) - chemistry , zinc , methanol , yield (engineering) , ethanol , hydrolysis , medicinal chemistry , nuclear chemistry , inorganic chemistry , crystallography , stereochemistry , organic chemistry , metallurgy , materials science
The pyrazolylborate−zinc complexes Tp Ph,Me Zn−H and Tp Ph,Me Zn−OH undergo insertion reactions with heterocumulenes. CO 2 , CS 2 and RNCS insert into the Zn−H function to yield the corresponding Zn−OCH(O), Zn−SCH(S) and Zn−SCH(NR) complexes. The primary products resulting from the insertion of CS 2 , COS and RNCS into the Zn−OH function undergo rearrangements and subsequent reactions. Tp Ph,Me Zn−OH and CS 2 or COS yield Tp Ph,Me Zn−SH and COS or CO 2 , whereas with RNCS the complexes Tp Ph,Me Zn−SC(O)NHR are formed. In the presence of alcohols these are incorporated in the Zn−OH insertion products: CS 2 /methanol yields Tp Ph,Me Zn−SC(S)OMe and RNCS/ethanol yields Tp Ph,Me Zn−SC(NR)OEt. All product types were characterized by X‐ray crystallography. The reactions and structures support the four‐centre reaction mechanism proposed for hydrolytic zinc enzymes.