Co-reporter:Mitsuyoshi Ochiai, Hisako Hashimoto and Hiromi Tobita
Dalton Transactions 2009 (Issue 10) pp:1812-1814
Publication Date(Web):27 Jan 2009
DOI:10.1039/B819229B
Reactions of a neutral silyleneruthenium complex with ketones and aldehydes, and isolation of their agostic intermediates are reported, where an α-H abstraction or hydrosilylation of the carbonyl compounds occurs depending on the substituents of the substrates.
Co-reporter:Masaaki Okazaki, Nobukazu Yamahira, Jim Josephus Gabrillo Minglana, Takashi Komuro, Hiroshi Ogino and Hiromi Tobita
Organometallics 2008 Volume 27(Issue 5) pp:918-926
Publication Date(Web):February 15, 2008
DOI:10.1021/om701194e
The reactions of [Ru(xantsil)(CO)(η6-C6H5CH3)] [1a, xantsil = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl))] with some electron-donating molecules were reported. When 1a was dissolved in benzene, benzene replaced the η6-toluene ligand easily at room temperature to give [Ru(xantsil)(CO)(η6-C6H6)] (1b). The η6-toluene ligand was also substituted by sterically less demanding two-electron donors smoothly at room temperature to afford [Ru(xantsil)(CO)L3] (L = CH3CN (2), tBuNC (3), and PMe3 (4)). The X-ray diffraction studies revealed that they take a typical octahedral geometry, in which the xantsil ligand is coordinated to the Ru(II) center in κ2(Si,Si) fashion. Reactions of 1a with sterically demanding phosphines gave [Ru(xantsil)(CO)(PR3)] (R = iPr (5) and Cy (6)). According to the X-ray diffraction study, complex 6 takes a square-pyramidal geometry, in which the xantsil ligand is bound to the Ru(II) center in κ3(Si,Si,O) fashion and one of the silyl groups occupies the apical position. The coordinatively unsaturated Ru(II) center is slightly stabilized by the agostic interaction by the C−H bonds in PCy3 [Ru···H: 2.89 and 3.06 Å]. The highly coordinatively unsaturated nature in 6 was indicated by the reaction with carbon monoxide molecules to give [Ru(xantsil)(CO)3(PCy3)] (7) at room temperature. The typical octahedral geometry with the κ2(Si,Si)-xantsil ligand was established by the X-ray diffraction study.
Co-reporter:Mitsuyoshi Ochiai;Hisako Hashimoto Dr.
Angewandte Chemie International Edition 2007 Volume 46(Issue 43) pp:
Publication Date(Web):21 SEP 2007
DOI:10.1002/anie.200703154
Ring around the RuSi: Abstraction of a pyridine ligand with BPh3 was used to synthesize the silylene complex 1 (see scheme), which reacts with nitriles at room temperature to give silylisocyanide complex 3 by CC bond activation. The structure of key intermediate 2 with an η2-SiH agostic interaction is given along with mechanisms for the formation of 2 and 3.
Co-reporter:Mitsuyoshi Ochiai;Hisako Hashimoto Dr.
Angewandte Chemie 2007 Volume 119(Issue 43) pp:
Publication Date(Web):21 SEP 2007
DOI:10.1002/ange.200703154
Ruthenium wird umringt: Die Abstraktion eines Pyridinliganden mit BPh3 wurde zur Synthese des Silylenkomplexes 1 genutzt (siehe Schema), der mit Nitrilen bei Raumtemperatur unter C-C-Aktivierung zum Silylisocyanidkomplex 3 reagiert. Die Struktur des Schlüsselintermediats 2 mit einer agostischen η2-Si-H-Wechselwirkung sowie die Mechanismen für die Bildung von 2 und 3 werden beschrieben.
Co-reporter:Rockshana Begum, Takashi Komuro and Hiromi Tobita
Chemical Communications 2006 (Issue 4) pp:432-433
Publication Date(Web):02 Dec 2005
DOI:10.1039/B512759A
The synthesis and characterization of tungsten and molybdenum complexes of the xanthene-based bis(silyl) ligand (xantsil) with a κ3(Si,Si,O) coordination mode are reported, where an insertion of tBuCN into a tungsten–silicon bond leads to formation of an η2-iminoacyl complex.
Co-reporter:Masaaki Okazaki, Kyeong A Jung and Hiromi Tobita
Chemical Communications 2005 (Issue 7) pp:912-914
Publication Date(Web):23 Dec 2004
DOI:10.1039/B413861A
Treatment of Cp*(CO)Fe{κ2(Si,P)-SiMe2PPh2} with methyl vinyl ketone gave a 1,2-addition product, Cp*(CO)Fe{κ2(Si,P)-SiMe2OCMe(CHCH2)PPh2}. A linear-type Cp*(CO)2FeSiMe2PPh2 also reacted with the ketone to yield a 1,4-addition product, Cp*(CO)2Fe{κ1(Si)-SiMe2OC(Me)CHCH2PPh2}, which was further converted to a seven-membered metallacycle, Cp*(CO)Fe{κ2(Si,P)-SiMe2OC(Me)CHCH2PPh2}, upon photolysis.
Co-reporter:Takahito Watanabe;Hisako Hashimoto Dr.
Angewandte Chemie 2004 Volume 116(Issue 2) pp:
Publication Date(Web):19 DEC 2003
DOI:10.1002/ange.200352383
Ein Hydridoligand, der eine WSi-Bindung überbrückt, ist in einem Hydrido(hydrosilylen)-Wolfram-Komplex (siehe Bild) und dessen η5-C5Me5-Analogon zu finden. Beide Verbindungen wurden durch Photolyse von [Cp′W(CO)3Me] (Cp′=η5-C5Me4Et, η5-C5Me5) in Gegenwart von H3SiC(SiMe3)3 synthetisiert. Die starke Wechselwirkung zwischen Hydrido- und Silylenligand wurde durch NMR-Spektroskopie und Röntgenstrukturanalyse belegt.
Co-reporter:Hiromi Tobita ;Akihisa Matsuda;Hisako Hashimoto Dr.;Keiji Ueno ;Hiroshi Ogino
Angewandte Chemie 2004 Volume 116(Issue 2) pp:
Publication Date(Web):19 DEC 2003
DOI:10.1002/ange.200352519
1,2- und 1,3-Gruppenwanderung: Der erste donorfreie Silyl(silylen)-Eisen-Komplex 1 wurde hergestellt und charakterisiert (siehe Schema). Dieser Komplex reagiert bei leichtem Erwärmen mit tBuNC unter Bildung des Disilanylkomplexes 2 durch 1,3-Alkyl- und Aryl- sowie 1,2-Silyl-Wanderung. 2 ist ein Beispiel dafür, wie Organosilicium-Spezies, die an Übergangsmetall-Zentren gebunden sind, in dynamischer Weise ihre Form ändern (Mes=2,4,6-Trimethylphenyl).
Co-reporter:Hiromi Tobita ;Akihisa Matsuda;Hisako Hashimoto Dr.;Keiji Ueno ;Hiroshi Ogino
Angewandte Chemie International Edition 2004 Volume 43(Issue 24) pp:
Publication Date(Web):9 JUN 2004
DOI:10.1002/anie.200490076
Co-reporter:Hiromi Tobita ;Akihisa Matsuda;Hisako Hashimoto Dr.;Keiji Ueno ;Hiroshi Ogino
Angewandte Chemie 2004 Volume 116(Issue 24) pp:
Publication Date(Web):9 JUN 2004
DOI:10.1002/ange.200490076
Co-reporter:Hiromi Tobita ;Akihisa Matsuda;Hisako Hashimoto Dr.;Keiji Ueno ;Hiroshi Ogino
Angewandte Chemie International Edition 2004 Volume 43(Issue 2) pp:
Publication Date(Web):19 DEC 2003
DOI:10.1002/anie.200352519
Facile 1,2- and 1,3-group migrations: The first donor-free silyl(silylene)–iron complex 1 has been prepared and structurally characterized (see scheme). This complex reacts with tBuNC under mild heating to give a disilanyl complex 2 through 1,3-alkyl and aryl migration and 1,2-silyl migration processes. Complex 2 is an example of how organosilicon species bound to transition-metal centers can change their form in a dynamic fashion (Mes=2,4,6-trimethylphenyl).
Co-reporter:Takahito Watanabe;Hisako Hashimoto Dr.
Angewandte Chemie International Edition 2004 Volume 43(Issue 2) pp:
Publication Date(Web):19 DEC 2003
DOI:10.1002/anie.200352383
A hydrido ligand bridging a WSi bond is present in a novel hydrido(hydrosilylene)–tungsten complex (see picture) and its η5-C5Me5 analogue, which were synthesized by photolysis of [Cp′W(CO)3Me] (Cp′=η5-C5Me4Et, η5-C5Me5) in the presence of H3SiC(SiMe3)3. This strong hydrido–silylene interligand interaction was revealed by NMR spectroscopic and X-ray structural analyses.
Co-reporter:Masatoshi Iwata, Masaaki Okazaki and Hiromi Tobita
Chemical Communications 2003 (Issue 21) pp:2744-2745
Publication Date(Web):08 Oct 2003
DOI:10.1039/B308885E
Heating a toluene solution of Cp*(CO)(C5H5N)FeSiMe2NPh2 led to insertion of pyridine into the iron–silicon bond to form Cp*(CO)Fe{η3(C,C,C)-C5H5NSiMe2NPh2}.
Co-reporter:Mitsuyoshi Ochiai, Hisako Hashimoto and Hiromi Tobita
Dalton Transactions 2009(Issue 10) pp:NaN1814-1814
Publication Date(Web):2009/01/27
DOI:10.1039/B819229B
Reactions of a neutral silyleneruthenium complex with ketones and aldehydes, and isolation of their agostic intermediates are reported, where an α-H abstraction or hydrosilylation of the carbonyl compounds occurs depending on the substituents of the substrates.
![TRIMETHYL-[SILYL-BIS(TRIMETHYLSILYL)METHYL]SILANE](http://img.cochemist.com/ccimg/72200/72190-67-1.png)
![TRIMETHYL-[SILYL-BIS(TRIMETHYLSILYL)METHYL]SILANE](http://img.cochemist.com/ccimg/72200/72190-67-1_b.png)
