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Si−H‐Functionalized Ferriodisiloxanes: Synthesis from the Ferriodimethylsilanols C 5 R 5 (OC) 2 Fe−SiMe 2 OH (R = H, Me) and Photoinduced Transformation into µ 2 ‐Disiloxanediyl‐Bridged Dinuclear Iron Complexes
Author(s) -
Malisch Wolfgang,
Hofmann Marco,
Kaupp Günter,
Käb Harald,
Reising Joachim
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(200212)2002:12<3235::aid-ejic3235>3.0.co;2-a
Subject(s) - chemistry , silanes , dimethyldioxirane , surface modification , hydrolysis , crystal structure , condensation , medicinal chemistry , condensation reaction , polymer chemistry , crystallography , catalysis , organic chemistry , silane , physics , thermodynamics
Hydrolysis of the ferriochlorosilanes C 5 R 5 (OC) 2 Fe−SiMe 2 Cl [R = H ( 1a ), Me ( 1b )] in the presence of Et 3 N yields the corresponding ferriosilanols C 5 R 5 (OC) 2 Fe−SiMe 2 (OH) ( 2a and 2b ). In addition, 2b is also obtained by oxo‐functionalization of C 5 Me 5 (OC) 2 Fe−SiMe 2 H ( 3 ) with dimethyldioxirane. The ferriosilanol 2a can be converted into the ferriodisiloxanes Cp(OC) 2 Fe−SiMe 2 OSiR 3 [R 3 Si = Me 2 (H)Si ( 5a ), p Tol 2 (H)Si ( 5b ), Me 3 Si ( 5c ) and p Tol(Me)(H)Si ( 5d )] by condensation with the chloro(organo)silanes R 3 SiCl ( 4a − d ). Irradiation of 5a and 5b results in CO elimination, followed by dimerization to give the cyclic 1,5‐diferratetrasiloxanes [µ 2 ‐SiMe 2 OSi(R) 2 ] 2 [Fe(H)(CO)Cp] 2 [R = Me ( 6a ) and p Tol ( 6b )]. Compounds 2b and 6b have been characterized by single‐crystal X‐ray structure determination. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)