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Cleavage of the Fe–Fe Bond of (Me 2 SiSiMe 2 )[η 5 ‐C 5 H 4 Fe (CO) 2 ] 2 with Na/Hg and Molecular Structure of the Ring‐Opened Complex
Author(s) -
Sun HudLin,
Zhang ZhenSheng,
Zhou XiuZhong
Publication year - 2003
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.20030210724
Subject(s) - chemistry , crystallography , bond length , bond cleavage , molecule , cleavage (geology) , ring (chemistry) , crystal structure , x ray crystallography , stereochemistry , molecular geometry , single bond , diffraction , catalysis , organic chemistry , group (periodic table) , geotechnical engineering , fracture (geology) , engineering , physics , optics
The reaction of the title cyclic complex (1) with sodium amalgam in THF resulted in the expected cleavage of the Fe—Fe bond to afford bis‐sodium salt (Me 2 SiSiMe 2 ) [η 5 ‐C 5 H 4 Fe (CO) 2 Na] 2 (4). The latter was not isolated and was used directly to react with MeI, PhCH 2 Cl, CH 3 C(O)Cl, PhC(O)Cl, Cy 3 SnCl (Cy = cyclohexyl) or Ph 3 SnCl to afford corresponding ring‐opened derivatives (Me 2 SiSiMe 2 ) [η5‐C 5 H 4 Fe (CO) 3 R] 2 [5, R=Me; 6, R = PhCH 2 ; 7, R = CH 3 C(O); 8, R = PhC (O); 9, R = Cy 3 Sn or 10, R = Ph 3 Sn]. The crystal and molecular structures of 10 were determined by X‐ray diffraction analysis. The molecule took the desired anti conformation around the Si—Si bond. The length of the Si—Si bond is 0.2343(3) nm, which is essentially identical to that in the cyclic structure of 1 [0.2346(4) nm]. This result unambiguously demonstrates that the Si—Si bond in the cyclic structure of 1 is not subject to obvious ring strain.