Synthesis and Reactivity of Silicon Transition Metal Complexes, 33. Metallo Silanols and Metallo Siloxanes, 8. Metallo‐silanole vom Typ C₅R₅(OC)₂(Me₃P)M—SiPh₂OH (M = Cr, Mo, W): Darstellung nach der Dimethyldioxiran‐Methode und Überführung in funktionalisierte Metallo‐disiloxane

Abstract

Synthesis and Reactivity of Silicon

Reactions of SiH-Functionalized Cyclopentadienes with Metal Carbonyls

“…The Mo−Si distance [2.6294(8) Å] in 15 is close to those of [{Mo(μ-η 2 -HSiEt 2 )(CO) 4 } 2 ] [2.6152(6) and 2.7093(6) Å] . The W−Si distances [2.6252(12) Å for 18 , 2.6235(16) Å for 20 ] are in the range of the tungsten−silyl bond distances (2.533−2.633 Å) in the structurally related silyltungsten complexes Cp*(CO) 2 (L)WSiR 3 (L = PR‘ 3 , pyridine). 2d,3c,l,o, This is the first report for this kind of cyclic dinuclear molybdenum and tungsten complex, although there are many examples for the iron and ruthenium analogues. , …”

Ruthenium Silyl Complexes Containing the Cp(PMe3)2Ru Moiety: Preparation, Substituent Effects, and Silylene Character in the Ru−Si Bond

“…Malisch and co-workers successfully prepared a wide variety of late transition metal silyl complexes of the type L n MSiX 3 (ML n = CpCr(CO) 3 , CpMo(CO) 3 , Cp*Mo(CO) 3 , CpMo(CO) 2 (PMe 3 ), Cp*Mo(CO) 2 (PMe 3 ), CpW(CO) 3 , Cp*W(CO) 3 , CpW(CO) 2 (PMe 3 ), Cp*W(CO) 2 (PMe 3 ), CpFe(CO) 2 , Cp*Fe(CO) 2 , CpRu(CO) 2 , Cp*Ru(CO) 2 ; SiX 3 = SiHCl 2 , SiHMeCl, SiHMe 2 , SiPhHCl, SiPh 2 H, etc.) by reacting metal anions with the corresponding chlorosilane in hydrocarbon solvent. − Controlled exchange reactions at silicon afforded a variety of metallohydrosilanes, − -fluorosilanes, -aminosilanes, , -silanols, ,− and -alkoxysilanes…”

Si−H-Functionalized Ferriodisiloxanes: Synthesis from the Ferriodimethylsilanols C5R5(OC)2Fe−SiMe2OH (R = H, Me) and Photoinduced Transformation into µ2-Disiloxanediyl-Bridged Dinuclear Iron Complexes

“…[2Ϫ5] In the context of our systematic studies on the reactivity of functionalized siliconϪtransition metal complexes [6Ϫ13] we have shown that metallosilanols with a direct MϪSi bond of the general type L n MϪSi(R) 3Ϫn (OH) n (n ϭ 1Ϫ3) [14Ϫ30] are characterized by remarkably high stability towards self-condensation, due to the electron-releasing effect of the metal fragment. This property has permitted the isolation of a number of transition metal substituted silanols, [14Ϫ26] mainly of the chromium and iron groups, including examples with stereogenic metal and silicon atoms [26] and even of metallosilanediols [27,28] and -silanetriols. [29,30] The reactivity of this special class of silanols has so far not been explored in detail.…”

“…Ϫ CO ϩ ], 248(26) [C 5 Me 5 (CO)Fe Ϫ SiH ϩ ], 191 (100) [C 5 Me 5 Fe ϩ ]. Cl (1a, 256 mg, 0.96 mmol), dissolved in 25 mL of Et 2 O, was treated with Et 3 N (144 mg, 1.44 mmol) and H 2 O (100 mg, 5.55 mmol).…”