Organometalloidal derivatives of the transition metals.  12.  Polysilane-metal interactions.  Photochemical deoligomerizations and base treatment migrations from iron to cyclopentadienyl ligands

Pannell, Keith H.; Cervantes, Jorge; Hernández, Carlos Vargas; Cassias, J. B.; Vincenti, Steven P.

doi:10.1021/om00136a039

Cited by 137 publications

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“…compounds. [2,3,[10][11][12] In fact, this mechanism was notably successful in explaining the redistribution reactions of various organosilicon, -germanium, and -phosphorus systems. [13][14][15] We have previously given direct experimental evidence for 1,2silyl-migration from Si to the metal M (A!B or D!B') via isolating complexes of the type B' or C, which are formed in reactions of complexes of type A or D. [2,3,16] Furthermore, we have observed fluxional behavior in the 1,3-migration of methyl groups on an externally donor-stabilized silyl(silylene)iron complex [Cp(CO)Fe( = SiMe 2 !…”

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confidence: 99%

Direct Evidence for Extremely Facile 1,2‐ and 1,3‐Group Migrations in an FeSi₂ System

et al. 2003

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The formation and high reactivity of transition-metal-element multiple bonds plays an important role in transitionmetal-catalyzed reactions, in particular, by facilitating the cleavage and formation of usually robust bonds. Olefin metathesis is a typical and very useful example of this type of reaction, in which carbene complexes, which have a metalcarbon double bond, are not only key intermediates but may also act as high-performance catalysts.[1] In contrast to metal-carbon multiple bonds, metal-element multiple bonds, where the element is from the third or subsequent row of the periodic table, have been much less widely investigated. Among them, silylene complexes, which possess a metal-silicon double bond, have been the most extensively studied, [2][3][4][5][6][7][8][9] but the mechanisms of their reactions remain rather unclear.Both ourselves and Pannell's group have insisted, through the generation of silyl(silylene) complexes with transition metals from groups 6 to 9 and the preparation of their donorstabilized forms, that 1,2-and 1,3-group migrations of these systems (Scheme 1) occur very easily under mild conditions, and cause the metal-catalyzed oligomerization/deoligomerization, isomerization, and redistribution of organosilicon Scheme 1. Illustrating the 1,2-and 1,3-group migrations in silyl(silylene) complexes with metals of groups 6 to 9.

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confidence: 99%

Direct Evidence for Extremely Facile 1,2‐ and 1,3‐Group Migrations in an FeSi₂ System

et al. 2003

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“…Pannel's group19 and our group20 reported that the irradiation of a disilanyliron complex 10 gave rise to a monosilyliron complex 11 (Fig. 4).…”

Section: Photochemical Reactions Of Disilanyl(carbonyl) Complexesmentioning

confidence: 90%

“…The 1,3‐R shift of the substituents has been observed in a number of mononuclear and dinuclear silyl(silylene) complexes 19–23,25. Two examples of this are discussed below.…”

Section: Photochemical Reactions Of Disilanyl(carbonyl) Complexesmentioning

confidence: 98%

“…4). Extensive mechanistic investigations19–24 revealed that the reaction is based on the mechanism shown in Figure 4. Irradiation causes the elimination of a carbonyl ligand, after which a 1,2‐silyl shift of the terminal silyl group to the iron atom occurs to produce the silyl(silylene) complex.…”

Section: Photochemical Reactions Of Disilanyl(carbonyl) Complexesmentioning

confidence: 99%

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Synthesis of Silylene and Silyl(silylene)metal Complexes

Ogino

2002

The Chemical Record

120

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In 1987, two research groups published the first-ever reports on the synthesis of silylene complexes and presented structural evidence. Since then, a range of synthetic methods have been developed and a number of silylene complexes have been prepared. In 1988, we reported on the first base-stabilized bis(silylene) complexes that can be regarded as being masked silyl(silylene) complexes. These complexes occupy a unique position among silylene and silyl(silylene) complexes in that they provide a convenient tool for studying the reactivity of coordinated silylenes. They are stable enough to be isolated, but the bond between the silylene silicon atom and the internal base can easily be cleaved by thermal perturbation to generate real silyl(silylene) complexes. To date, a number of base-stabilized bis(silylene) complexes have been prepared in which the central metals range from group 5 to group 9. Only two base-free silyl(silylene) complexes have been prepared. One is prepared by reacting a platinum complex with a stable silylene; the other is produced by the photolysis of a tungsten complex in the presence of a hydrodisilane.

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“…Four-centered transition states are also postulated to be involved in the 1,3-migration of R groups on silyl(silylene) complexes A (Chart 1). 3,4 Since this 1,3-migration involves activation of usually robust Si−X σ-bonds (X  H, C, O, etc. ), it is regarded as one of the fundamental processes for transformations of silicon compounds.…”

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Isolation of a Hydrogen-Bridged Bis(silylene) Tungsten Complex: A Snapshot of a Transition State for 1,3-Hydrogen Migration

et al. 2015

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A hydrogen-bridged bis(silylene) complex, which can be viewed as a snapshot of a transition state for 1,3-hydrogen migration, was isolated, and its unprecedented WSi2H four-membered-ring structure with a short diagonal Si-Si distance was revealed by X-ray crystallography. NMR studies including determination of the W-Si, Si-Si, and Si-H coupling constants and theoretical calculations suggest that a novel multicenter bond is formed in the WSi2H system, in which the bridging hydrogen takes on a hydridic nature.

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Organometalloidal derivatives of the transition metals. 12. Polysilane-metal interactions. Photochemical deoligomerizations and base treatment migrations from iron to cyclopentadienyl ligands

Cited by 137 publications

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Direct Evidence for Extremely Facile 1,2‐ and 1,3‐Group Migrations in an FeSi₂ System

Direct Evidence for Extremely Facile 1,2‐ and 1,3‐Group Migrations in an FeSi₂ System

Synthesis of Silylene and Silyl(silylene)metal Complexes

Isolation of a Hydrogen-Bridged Bis(silylene) Tungsten Complex: A Snapshot of a Transition State for 1,3-Hydrogen Migration

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Organometalloidal derivatives of the transition metals. 12. Polysilane-metal interactions. Photochemical deoligomerizations and base treatment migrations from iron to cyclopentadienyl ligands

Cited by 137 publications

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Direct Evidence for Extremely Facile 1,2‐ and 1,3‐Group Migrations in an FeSi2 System

Direct Evidence for Extremely Facile 1,2‐ and 1,3‐Group Migrations in an FeSi2 System

Synthesis of Silylene and Silyl(silylene)metal Complexes

Isolation of a Hydrogen-Bridged Bis(silylene) Tungsten Complex: A Snapshot of a Transition State for 1,3-Hydrogen Migration

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Direct Evidence for Extremely Facile 1,2‐ and 1,3‐Group Migrations in an FeSi₂ System

Direct Evidence for Extremely Facile 1,2‐ and 1,3‐Group Migrations in an FeSi₂ System