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Experimental and Theoretical Studies of Unusual Four‐Membered Metallacycles from Reactions of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes with the Sulfurdiimide Me 3 SiN=S=NSiMe 3
Author(s) -
Kaleta Katharina,
Ruhmann Martin,
Theilmann Oliver,
Roy Subhendu,
Beweries Torsten,
Arndt Perdita,
Villinger Alexander,
Jemmis Eluvathingal D.,
Schulz Axel,
Rosenthal Uwe
Publication year - 2012
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.201101188
Subject(s) - chemistry , trimethylsilyl , acetylene , metallocene , pyridine , ring (chemistry) , metal , group (periodic table) , crystallography , group 2 organometallic chemistry , medicinal chemistry , stereochemistry , molecule , organic chemistry , polymerization , polymer
The use of the sulfurdiimide RN=S=NR′ (R = R′ = SiMe 3 , 3 ) in reactions with group 4 metallocene bis(trimethylsilyl)acetylene complexes of the type [Cp 2 M(L)(η 2 ‐Me 3 SiC 2 SiMe 3 )] ( 1 : M = Ti, no L; 2 : M = Zr, L = pyridine) has led to the formation of four‐membered metallacycles 4M containing the group 4 metal, nitrogen and sulfur. DFT calculations performed on compound 4Ti indicate that this complex is best described as a σ‐complex with cyclic delocalisation of the ring electrons. Moreover, pseudo‐Jahn–Teller distortion plays a significant role in stabilising this complex.