Metallosilanediols of molybdenum and tungsten. Synthesis and transformation to functionalized metallotrisiloxanes. Hydrogen-bonded structure of [(C5Me5)(OC)2(Me3P)MO–SiMe(OH)2]

Malisisch, Wolfgang; Lankat, Reiner; Fey, Oliver; Reising, Joachim; Schmitzer, Siegfried

doi:10.1039/c39950001917

Cited by 24 publications

(6 citation statements)

References 17 publications

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“…The Mo-Si bonds (2.4804(9) and 2.4795(9) Å for 1a; 2.4996(9) and 2.5008(9) Å for 1b) are shorter than those of the known silylmolybdenum complexes (2.51-2.67 Å). 29, [39][40][41] The Cr-Si bond length of 2 (2.355(2) Å) is comparable to or shorter than those of the reported alkyl-and arylsilylenechromium complexes (2.36-2.53 Å). 2,30 The short metal-silicon bond 43,44 and that of H 2 SirOH 2 (2.10-2.13 Å) 43,44 and between that of H 3 Si-NH 2 (1.72 Å) 43 and that of H 2 SirNH 3 (2.04-2.09 Å), 43,45 respectively.…”

Section: Resultssupporting

confidence: 54%

Synthesis, Crystal Structures, and Fluxional Behavior of Donor-Bridged Bis(silylene)molybdenum and -chromium Complexes

Ueno

Masuko

1999

Organometallics

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Donor-bridged bis(silylene)molybdenum and -chromium complexes CpM(CO) 2 {(SiMe 2 )‚‚‚ Do‚‚‚(SiMe 2 )} (Cp ) η-C 5 H 5 ; M ) Mo, Do ) OMe (1a); M ) Mo, Do ) NEt 2 (1b); M ) Cr, Do ) OMe (2)) were synthesized by photolysis of a C 6 D 6 solution containing CpM(CO) 3 Me and HSiMe 2 SiMe 2 Do. The X-ray crystal structures of 1a, 1b, and 2 revealed that the M-Si bonds (2.4795(9) and 2.4804(9) Å for 1a, 2.4996(9) and 2.5008(9) Å for 1b, and 2.355(2) Å for 2) are significantly shorter than those of structurally similar silylmolybdenum and -chromium complexes, while the Si-O bonds in 1a (1.782(2) and 1.788(3) Å) and 2 (1.788(3) Å) and the Si-N bonds in 1b (1.933(2) and 1.923(3) Å) are much longer than usual Si-O and Si-N single bonds. These structural data indicate that the M-Si bonds bear partial double-bond character, whereas the Si-O and Si-N bonds are regarded as a hybrid of covalent bonding and dative bonding. The unsaturated nature of the metal-silicon bonds is also shown by the significant downfield shift of the 29 Si NMR signals (1a, δ ) 117.6 ppm; 1b, δ ) 80.5 ppm; 2, δ ) 128.6 ppm) compared to those of structurally similar silylmolybdenum and -chromium complexes. Complexes 1a, 1b, and 2 showed fluxional behavior due to silylenemethyl group exchange and, in the case of 1b, N-Et group exchange. A mechanism involving the generation of a base-free silyl(silylene) complex as the key intermediate is proposed to explain the fluxional process.

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Section: Resultssupporting

confidence: 54%

Synthesis, Crystal Structures, and Fluxional Behavior of Donor-Bridged Bis(silylene)molybdenum and -chromium Complexes

Ueno

Masuko

1999

Organometallics

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“…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…”

Section: Introductionmentioning

confidence: 99%

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

1999

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The preparation and characterization of new ruthenium(II) silyl complexes containing the Cp(PM3)2Ru moiety are described. The ruthenium(II) hydride Cp(PMe3)2RuH reacts with a variety of chlorosilanes to produce the ruthenium(II) silyl complexes Cp(PMe3)2RuSiR3 [SiR3 = SiCl3 (1), SiHCl2 (2), SiH2Cl (3), SiMeCl2 (4), SiMeHCl (5), SiMe2Cl (6)] and the ruthenium(IV) dihydride [Cp(PMe3)2RuH2]Cl. Silyl complexes 1−6 undergo chloride/hydride exchange with LiAlH4 to give the corresponding ruthenium(II) hydrosilyl complexes Cp(PMe3)2RuSiHR2 [SiHR2 = SiH3 (7), SiMeH2 (8), SiMe2H (9)]. Methylation of 6 with AlMe3 produces Cp(PMe3)2RuSiMe3 (10). A method for recovering the Cp(PMe3)2Ru moiety is described. The structure of 1 was determined by X-ray crystallography. Complexes 1−10 represent the first complete set of metal silicon compounds that contain every possible combination of H, Cl, and Me groups on silicon. The effects of the substituents on the spectroscopic properties of 1−10 were examined as a function of Tolman's electronic parameter (χ i ) for the substituents on silicon. The infrared stretching frequency, ν(Si−H), and the NMR coupling constants, 2 J SiP and 1 J SiH, exhibit a linear relationship with ∑χ i , consistent with Bent's rule. However, when the NMR resonances SiR3 δ(29Si), SiH δ(1H), and SiMe δ(13C) were examined as a function of ∑χ i , the silyl groups differentiated into three classes: dichlorosilyl, monochlorosilyl, and “non-chlorosilyl”; within each class a linear but inverse relationship with ∑χ i was observed. Silylene character in the Ru−Si bond resulting from d(Ru)−σ*(Si−Cl) π-back-bonding interactions was used to explain the origin of the three silyl classes.

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“…[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.…”

Section: Introductionmentioning

confidence: 99%

“…( Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002) of the SiH unit to electronically unsaturated metal centres to provide access to SiϪOϪSi-bridged dinuclear metal complexes. [27] This was strong motivation to perform the synthesis of novel metallosilanols, especially with the well-known iron fragments C 5 R 5 (OC) 2 Fe (R ϭ H, Me), and condensation reactions to afford the corresponding disiloxanes. Furthermore, the SiH-functional derivatives were used for photoinduced transformation, providing novel eight-membered cyclic dimetallasiloxanes.…”

Section: Introductionmentioning

confidence: 99%

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

Malisch

Hofmann

Kaupp

et al. 2002

Eur. J. Inorg. Chem.

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Hydrolysis of the ferriochlorosilanes C5R5(OC)2Fe−SiMe2Cl [R = H (1a), Me (1b)] in the presence of Et3N yields the corresponding ferriosilanols C5R5(OC)2Fe−SiMe2(OH) (2a and 2b). In addition, 2b is also obtained by oxo‐functionalization of C5Me5(OC)2Fe−SiMe2H (3) with dimethyldioxirane. The ferriosilanol 2a can be converted into the ferriodisiloxanes Cp(OC)2Fe−SiMe2OSiR3 [R3Si = Me2(H)Si (5a), pTol2(H)Si (5b), Me3Si (5c) and pTol(Me)(H)Si (5d)] by condensation with the chloro(organo)silanes R3SiCl (4a−d). Irradiation of 5a and 5b results in CO elimination, followed by dimerization to give the cyclic 1,5‐diferratetrasiloxanes [µ2‐SiMe2OSi(R)2]2 [Fe(H)(CO)Cp]2 [R = Me (6a) and pTol (6b)]. Compounds 2b and 6b have been characterized by single‐crystal X‐ray structure determination. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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Metallosilanediols of molybdenum and tungsten. Synthesis and transformation to functionalized metallotrisiloxanes. Hydrogen-bonded structure of [(C₅Me₅)(OC)₂(Me₃P)MO–SiMe(OH)₂]

Cited by 24 publications

References 17 publications

Synthesis, Crystal Structures, and Fluxional Behavior of Donor-Bridged Bis(silylene)molybdenum and -chromium Complexes

Synthesis, Crystal Structures, and Fluxional Behavior of Donor-Bridged Bis(silylene)molybdenum and -chromium Complexes

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

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

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Metallosilanediols of molybdenum and tungsten. Synthesis and transformation to functionalized metallotrisiloxanes. Hydrogen-bonded structure of [(C5Me5)(OC)2(Me3P)MO–SiMe(OH)2]

Cited by 24 publications

References 17 publications

Synthesis, Crystal Structures, and Fluxional Behavior of Donor-Bridged Bis(silylene)molybdenum and -chromium Complexes

Synthesis, Crystal Structures, and Fluxional Behavior of Donor-Bridged Bis(silylene)molybdenum and -chromium Complexes

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

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

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Metallosilanediols of molybdenum and tungsten. Synthesis and transformation to functionalized metallotrisiloxanes. Hydrogen-bonded structure of [(C₅Me₅)(OC)₂(Me₃P)MO–SiMe(OH)₂]

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