Photochemical Reaction of CpFe(CO)₂SiMe₃ (Cp = η⁵-C₅H₅) with a Trihydrosilane Containing a Bulky Amino Substituent, Bis(trimethylsilyl)aminosilane

Abstract

A photochemical reaction between CpFe(CO)2SiMe3 and (Me3Si)2NSiH3 in hexane gave the silylyne-bridged triiron complex Cp3Fe3(CO)4SiN(SiMe3)2 (2) and a diiron complex bridged by a four-membered cyclic silylene, Cp2Fe2(CO)2(μ-CO)(μ-SiN(SiMe3)2SiMe2CH2) (3). In contrast, the silylene- and alkyne-bridged triiron complex Cp3Fe3{μ2-SiHN(SiMe3)2}{μ3-COSiH2N(SiMe3)2}{μ3-η2-C2O2-SiHN(SiMe3)2} (4) was formed as the main product by a similar reaction in toluene.

A triangular triplatinum(0) complex with bridging germylene ligands: insertion of alkynes into the Pt–Ge bond rather than the Pt–Pt bond

“…The coordination of the electron-releasing germylene ligands with the Pt(0)-phosphine units composed of the d 10 configuration may enhance the reactivity for the alkyne insertion into the Pt-Ge bond. Several research groups have employed silylene and germylene ligands in the synthesis of multinuclear complexes of Fe, 15 Ru, 16 Os, 17 Rh, 18 Ir, 19 Ni, 20 Pd, 21 Pt, 22 and Au. 23 The reactivities of these complexes, however, were reported in only a part of them.…”

A Generic One‐Pot Route to Acyclic Two‐Coordinate Silylenes from Silicon(IV) Precursors: Synthesis and Structural Characterization of a Silylsilylene

“…[7] A convenient synthetic attribute of this compound is its direct formation from the Si IV precursor Si{N(SiMe 3 )Dipp}Br 3 (1; Dipp = 2,6-iPr 2 C 6 H 3 ) and two equivalents of (thf) 2 Li{B(NDippCH) 2 }. [12] In the case of bulkier nucleophiles, redox properties are important; thus, although 1 is unreactive towards sterically encumbered alkali metal amides, such as Li{N(SiMe 3 )Dipp} or K{N(SiMe 3 ) 2 }, it reacts readily with two equivalents of (thf) 2 Li{B(NDippCH) 2 } or (thf) 2 K[Si(SiMe 3 ) 3 ], or three equivalents of K[CPh 3 ], generating BrB(NDippCH) 2 , [7] BrSi(SiMe 3 ) 3 , and Gombergs dimer, respectively. To better understand this method and its scope for the direct conversion of Si IV halides into acyclic silylenes, we have investigated the reactivity of 1 towards other sterically encumbered anionic main group and transition metal nucleophiles.…”

“…Thus, although the reaction of 1 with K[CpFe(CO) 2 ] primarily yields the coupling product 2, a small quantiy of the Fe À Si containing system {CpFe(CO)} 2 (m-CO)(m-SiBr{N(SiMe 3 )Dipp}), was also isolated (see the Supporting Information). [12] In the case of bulkier nucleophiles, redox properties are important; thus, although 1 is unreactive towards sterically encumbered alkali metal amides, such as Li{N(SiMe 3 )Dipp} or K{N(SiMe 3 ) 2 }, it reacts readily with two equivalents of (thf) 2 Li{B(NDippCH) 2 } or (thf) 2 K[Si(SiMe 3 ) 3 ], or three equivalents of K[CPh 3 ], generating BrB(NDippCH) 2 , [7] BrSi(SiMe 3 ) 3 , and Gombergs dimer, respectively.…”

Organometallic chemistry of bi- and poly-metallic complexes

“…The process of phosphorus ligand migration has been shown to occur using diiron complexes (14) containing asymmetric bridges between the two cyclopentadienyl ligands, which is similar to carbonyl migration but much slower due to a higher energy requirement. 66 The photochemical reaction between [(Z 5 -C 5 H 5 )Fe(CO) 2 -SiMe 3 ] and (Me 3 Si) 2 NSiH 3 gave the unprecedented complexes [(Z 5 67 The thermolytic reactions of cyclooctatetraene-(COT) and 7H-indene-coordinated diiron bridging carbene complexes have been investigated and found to be greatly influenced by the different cycloolefin and bridging carbene units. 68 A new route to the m-vinyliminium complexes (15) involving alkyne-isocyanide coupling in [(Z 5 -C 5 H 5 ) 2 Fe 2 (CNMe)(CO) 3 {m-CQN(Me)R}] has been developed.…”