Facile 1,2-Migration of a Methyl Group on a {Dimethoxy(methyl)silyl}tungsten Complex: Formation of a Base-Stabilized (Dimethoxysilylene)(methyl) Complex

Suzuki, Eiji; Komuro, Takashi; Kanno, Yuto; Okazaki, Masanori; Tobita, Hiromi

doi:10.1021/om100399s

Cited by 20 publications

(14 citation statements)

References 34 publications

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“… 22 R = t Bu-2,6-[P(O)(O i Pr) 2 ] 2 C 6 H 2 - 23 Additional derivative, R = Me 24 cis - 5-29 converts to the trans -form in solution over 3 days …”

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

Reactions of Hydrosilanes with Transition Metal Complexes

2016

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This third review in a series involving reactions of hydrosilanes and transition metal complexes and characterization of the products covers the period 2009 thru 2013. After a brief discussion of other synthetic methods used for the formation of Si-TM complexes, Section 3 provides an extended discussion of the types of ligands and metal complexes used as reactants with hydrosilanes. The increase in use of pincer ligands in forming stable, isolable complexes is featured. Three tables list the complexes reported for primary, secondary, and tertiary silanes. Many reactions leading to SiTM complexes are initiated by loss of a ligand prior to oxidative addition of the hydrosilane or by a metathesis reaction. Structural data are tabulated for the isolated complexes and provide the Si-TM bond ranges for the elements in the "d" block. A major section on nonclassical (σ or agostic) complexes includes two general groupings with Si-H···TM and M-H···Si interactions. A section on solution processes identified by NMR spectroscopy is dominated by hydride exchange examples. A section on bonding outlines a unifying bonding description that has been proposed as well as calculations reported for Si-TM complexes, both real and hypothetical examples.

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“… 22 R = t Bu-2,6-[P(O)(O i Pr) 2 ] 2 C 6 H 2 - 23 Additional derivative, R = Me 24 cis - 5-29 converts to the trans -form in solution over 3 days …”

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

Reactions of Hydrosilanes with Transition Metal Complexes

2016

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“…As a first step to demonstrating migration with larger groups, the Tobita group investigated 1,2‐methyl and 1,2‐aryl migration from W to Si in a range of silylenes. [ 62 , 63 , 64 , 65 ] Work on reversible aryl migrations, which is summarised in Scheme 9 , resulted in the isolation of the aryl migration intermediate – a silicon analogue of an η 3 ‐benzyl complex ( 26 ) – for both W and Mo. [ 64 , 65 ]…”

Section: Elementary Reactions and Cooperativitymentioning

confidence: 99%

Cooperativity in Transition Metal Tetrylene Complexes

Somerville

Campos

2021

Eur J Inorg Chem

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Cooperative reactivity between transition metals and ligands, or between two metals, has created significant opportunities for the development of new transformations that would be difficult to carry out with a single metal. Here we explore cooperativity between transition metals and divalent heavier group 14 elements (tetrylenes), a less‐explored facet of the field of cooperativity. Tetrylenes combine their strong σ‐donor properties with an empty p‐orbital that can accept electron density. This ambiphilicity has allowed them to form metal tetrylene and metallotetrylene complexes that place a reactive site adjacent to the metal. We have selected examples to demonstrate what has been achieved so far regarding cooperative reactivity, as this already spans metal‐, tetrylene‐ or multi‐site‐centred bond cleavage, cycloaddition, migration, metathesis, and insertion. We also highlight some challenges that need to be overcome for this cooperativity to make it to catalysis.

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“…The 29 Si NMR chemical shifts are very downfield (201.8 and 320.1ppm respectively) and the IR bands for the carbonyls appear at frequencies intermediate between those of alkylidynes and the known germylidene analogue, indicating that the degree of carbonyl backbonding is greater in the carbon compound. 104 A similar ligand stabilising strategy was employed in the preparation of a dmap-stabilised tungsten silylene as Cp*(CO) 2 W(4-Me-C 6 H 4 ){Si(4-Me-C 6 H 4 )(R)}.dmap (R = Me or 4-Me-C 6 H 4 ) which reacts with nitriles to yield silyliminoacyl tungsten complexes 105 and in the formation of dmap-stabilised iridium silylene complexes. 106 The use of transition metal complexes as catalysts in hydrosilylation reactions makes the addition of silanes to metal complexes a reaction of special interest.…”

Section: M(14)-transition Metalmentioning

confidence: 99%

Carbon, silicon, germanium, tin and lead

Parr

2011

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Facile 1,2-Migration of a Methyl Group on a {Dimethoxy(methyl)silyl}tungsten Complex: Formation of a Base-Stabilized (Dimethoxysilylene)(methyl) Complex

Cited by 20 publications

References 34 publications

Reactions of Hydrosilanes with Transition Metal Complexes

Reactions of Hydrosilanes with Transition Metal Complexes

Cooperativity in Transition Metal Tetrylene Complexes

Carbon, silicon, germanium, tin and lead

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