Arenechromiumtricarbonyl complexes of silyl(germyl)(stannyl)- and silyl(germyl)(plumbyl)methanes including the unexpected formation of arenechromiumtricarbonyldimethylsilanol, (η6-C6H5)Cr(CO)3SiMe2OH

Abstract

Treatment of PhMe 2 SiCH 2 GeMe 3 (1) with t-BuLi followed by addition of Me 3 ECl, E = Sn, Pb, results in the formation of phenylsilyl(germyl)stannyl-and phenylsilyl(germyl)plumbyl-methanes, PhMe 2 Si(Me 3 Ge)(EMe 3 )CH, E = Sn (2), Pb (3). The thermal reaction of 1, 2 and 3 with Cr(CO) 6 yields the corresponding aryl-Cr(CO) 3 analogs, {(η 6 -C 6 H 5 )Cr(CO) 3 }Me 2 Si(Me 3 Ge)CH 2 (4) and {(η 6 -C 6 H 5 )Cr(CO) 3 }Me 2 Si(Me 3 Ge)(EMe 3 )CH, E = Sn (5), Pb (6). The thermal treatment of 2 with Cr(CO) 6 in wet THF/di-n-butyl ether mixture results in the formation of the arenechromiumtricarbonyl silanol {(η 6 -C 6 H 5 )Cr(CO) 3 }Me 2 SiOH (7) which exhibits amphiphilic character, forming H-bonded chains in the solid state in a head-to-head arrangement of the areneCr(CO) 3 units.

Aryl Oligogermanes as Ligands for Transition Metal Complexes

“…In order to improve the yields and simplify the isolation of the desired compounds, a new set of conditions was investigated. Cr(CO) 6 ( 1a ) was treated with Ph 3 GeGePh 3 ( 5 ) and (C 6 F 5 ) 3 GeGePh 3 ( 6 ) in a mixture of ( n Bu) 2 O/THF (10:1) at reflux, (Scheme ). Similar conditions have been reported for the synthesis of group 14 derivatives using DME or dyglime .…”

Polysiloxanes Bearing Pendant Redox-Active Dendritic Wedges Containing Ferrocenyl and (η6-Aryl)tricarbonylchromium Moieties

“…The π-coordinating ability of the two electron-rich phenyl rings in 5 toward transition metals represented an alternative synthetic access to the targeted mixed ferrocenyl-chromium molecule 6 (Scheme , path A, top). For this purpose, we reacted bimetallic 5 with chromium hexacarbonyl in the donor medium n -dibutyl ether/THF, which after appropriate purification afforded the desired doubly η 6 -complexed heterotetrametallic disiloxane 6 in reasonable yield …”