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

Abstract

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)

Protonation of Ferrocene: A Low‐Temperature X‐ray Diffraction Study of [Cp2FeH](PF6) Reveals an Iron‐Bound Hydrido Ligand

“…Iron–hydride distances determined by X‐ray diffraction are, by nature, shorter. A search in the CSD (ConQuest 1.19, 2017) database of related Cp iron hydrides revealed Fe–H distances ranging from 1.34 Å to 1.59 Å . The structures determined from the two data sets recorded at 30 K and 100 K revealed slightly bent ferrocene backbones (see Table ).…”

Reactions of Hydrosilanes with Transition Metal Complexes and Characterization of the Products

“…178a 82 Additional derivatives: mer-(OC) 3 (Ph 3 P)Fe(H)SiPhMeSiPhMeH as a 10:9 mixture of diastereomers and mer-(OC) 3 (Ph 3 P)Fe(H)SiPh 2 SiMe 3 . 166 179 Signals for the 29 Si NMR resonance for Si(p-Tol) 2 were not observed. 86 The product from step "a", [Cp*Ru(η 6 -C 6 H 5 -SiPh 2 -OH]BF 4 ], a yellow solid, was isolated in 86% yield and then reacted with the NaBPh 4 /MeOH.…”

Synthesis, Structural Characterization and Reactivity of the (Ferriomethyl)silanols C5R5(OC)2Fe−CH2−SiMe(R′)OH (R = H, Me; R′ = Me, Ph)

“…The stability of this type of metal fragment substituted silanols with respect to self-condensation is reduced, compared with the ferriosilanols C 5 R 5 (OC) 2 FeϪSiMe 2 OH (R ϭ H, Me) [1] bearing the SiϪOH unit directly at the transition metal atom. As a consequence, the silanol 4a undergoes condensation to a disiloxane, which is well known Eur.…”

“…The chemical shifts in the 29 Si NMR spectra [δ ϭ 21.8 (4a), 11.7 (4b), 21.1 (4c) ppm] reveal a decreased influence of the transition metal fragment on the silicon atom in the β-position. For example, in the case of 4a, the signal is shifted by approximately 44 ppm to a higher field compared with its counterpart Cp(OC) 2 FeϪSiMe 2 OH (δ ϭ 66.1 ppm) [1] without a methylene bridge.…”

“…[65] In contrast to the structures of other diorgano(metallo)silanols L n MϪSiR 2 OH, which prefer hydrogen-bonded ''dimerization'', e.g. C 5 Me 5 (OC) 2 FeϪSiMe 2 OH [1] and C 5 Me 5 -(OC) 2 RuϪSi(o-Tol) 2 OH, [26] in the case of the (ferriomethyl)-silanols 4a,b strong intermolecular OH···O bridges lead to the formation of discrete tetrameric units in the solid state, indicated by O···O distances of 2.7320(16)/2.7410(17) (4a) and 2.6965(17) Å (4b). This arrangement is similar to that found for Ph 3 SiOH.…”