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Reactivity of a Seven‐Membered Zirconacyclocumulene towards CN Multiple Bonds – Formation of Metallaheterocycles by Insertion of C≡N and C=N Groups
Author(s) -
Burlakov Vladimir V.,
Becker Lisanne,
Bogdanov Vyacheslav S.,
Andreev Maxim V.,
Arndt Perdita,
Spannenberg Anke,
Baumann Wolfgang,
Rosenthal Uwe
Publication year - 2014
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.201402618
Subject(s) - chemistry , metallacycle , alkyne , reactivity (psychology) , nitrile , ring (chemistry) , insertion reaction , crystal structure , stereochemistry , cyanide , medicinal chemistry , cyclopentadiene , pyrimidine , crystallography , coupling reaction , catalysis , x ray crystallography , organic chemistry , medicine , physics , alternative medicine , pathology , diffraction , optics
The reactions of the seven‐membered zirconacyclocumulene [Cp 2 Zr{η 4 ‐Me 3 SiC 4 (SiMe 3 )–C(C 2 SiMe 3 )=CSiMe 3 }] ( 1 ) with nitriles (RC≡N, R = Me, Ph) started with an insertion of a cyanide group into the metal–butadiyne bond followed by an alkyne–nitrile coupling and formation of 1‐zircona‐2‐azacyclopenta‐2,4‐dienes. The reaction product for R = Me is stabilized by dimerization to give a compound containing a four‐membered –N–Zr–N–Zr– ring and two identical five‐membered 1‐metalla‐2‐aza‐cyclopentadiene rings. In case of R = Ph, a metallacycle could not be isolated, and a pyrimidine was formed. The catalytic potential of this reaction was investigated. For PhN=C(H)Ph, again after insertion and coupling, a corresponding 1‐zircona‐2‐azacyclopenta‐4‐ene was established. The reaction of this compound with carbon dioxide led to ring expansion and formation of a seven‐membered product, which released CO 2 at higher temperature and to give back the reactant. The above‐mentioned products were characterized by NMR spectroscopy and single‐crystal X‐ray structure analysis.