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Regiospecific Hydroxylation of Metallodisilanes of the Iron Group – An Impressive Example of the Transition Metal Effect
Author(s) -
Malisch Wolfgang,
Jehle Heinrich,
Möller Stephan,
SahaMöller Chantu,
Adam Waldemar
Publication year - 1998
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/(sici)1099-0682(199811)1998:11<1585::aid-ejic1585>3.0.co;2-7
Subject(s) - chemistry , hydroxylation , yield (engineering) , disilane , medicinal chemistry , dimethyldioxirane , transition metal , hydrolysis , silicon , organic chemistry , catalysis , enzyme , materials science , metallurgy
Reaction of the ferriodisilanes C 5 R 5 (OC) 2 Fe–Si 2 H 5 [R = H ( 1a ), Me ( 1b )] with dimethyldioxirane leads to selective insertion of oxygen into the α‐Si–H bonds to yield the ferriodihydroxydisilanes C 5 R 5 (OC) 2 Fe–Si(OH) 2 –SiH 3 [R = H ( 2a ), Me ( 2b )]. Another access to yield 2a is opened by hydrolysis of the dichloro(ferrio)disilane Cp(OC) 2 Fe–SiCl 2 –SiH 3 ( 3a ). Treatment of the pentachloro(metallo)disilanes C 5 H 5 (OC) 2 Fe–Si 2 Cl 5 ( 4a ) and C 5 Me 5 (OC) 2 Ru–Si 2 Cl 5 ( 4b ) with water results in regiospecific hydroxylation of the β‐silicon atom to generate metallodisilanetriols C 5 R 5 (OC) 2 M–SiCl 2 –Si(OH) 3 [M = Fe, R = H ( 5a ); M = Ru, R = Me ( 5b )]. Controlled condensation of 5b with Me 2 Si(H)Cl leads to the novel rutheniosiloxane C 5 Me 5 (OC) 2 Ru–SiCl 2 –Si(OSiMe 2 H) 3 ( 6 ).