Easy oxidatively induced silicon–carbon bond activation in organoplatinum chemistry

Safa, Muhieddine A.; Jennings, Michael C.; Puddephatt, Richard J.

doi:10.1039/b927248h

Cited by 14 publications

(16 citation statements)

References 21 publications

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“…Noteworthy activation processes have also been documented by Puddephatt's group, who reported on the cleavage of C aryl −S bonds by [PtMe 2 (dimethylsulfide)] 2 leading to polymethylated SMe − bridged bimetallic compounds . Carbon–silicon bond activation under oxidative conditions has also been described …”

Section: Synthesis and Structures: A Systematic Overview Of D‐block Ementioning

confidence: 70%

Methyl Complexes of the Transition Metals

Campos

López‐Serrano

Peloso

et al. 2016

Chemistry A European J

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Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, i.e. based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition metal complexes containing M-CH3 fragments. Taking into account the impressive amount of data that are continuously provided by organometallic chemists in this area, this review is mainly focused on results of the last 5 years. After a panoramic overview on M-CH3 compounds of groups 3 to 11 which includes the most recent landmark findings in this area, two further sections are dedicated to methyl-bridged complexes and reactivity.

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Section: Synthesis and Structures: A Systematic Overview Of D‐block Ementioning

confidence: 70%

Methyl Complexes of the Transition Metals

Campos

López‐Serrano

Peloso

et al. 2016

Chemistry A European J

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“…Puddephatt et al reported a related oxidation involving SiÀ C bond cleavage. [102] [94,96,97] and NNO-ligated [98] Pt II complexes. Scheme 18.…”

Section: Aerobic Oxidation Of Pt II Complexes To Pt Ivmentioning

confidence: 99%

“…Puddephatt et al. reported a related oxidation involving SiC bond cleavage 102. Adding O 2 to a solution of [(bps)PtMe 2 ] ( 73 , bps=Me 2 Si(2‐C 5 H 4 N) 2 , Scheme ) in MeOH resulted in the formation of [(HOSiMe(2‐C 5 H 4 N) 2 )PtMe 3 ][OMe] ( 74 ).…”

Section: Stoichiometric Reactions Of Ptii With O2mentioning

confidence: 99%

Reactions of Pd and Pt Complexes with Molecular Oxygen

Scheuermann

Goldberg

2014

Chemistry A European J

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Knowledge of exactly how metal complexes react with molecular oxygen is still limited and this has hampered efforts to develop catalysts for oxidation reactions using O2 as the oxidant and/or oxygen-atom source. A better understanding of the reactions of different types of metal complexes with O2 will be of great utility in rational catalyst development. Reactions between molecular oxygen and Pd(0-II) and Pt(0-IV) complexes are reviewed here.

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“…In this regard, the metal catalyzed hydrolysis and alcoholysis of hydrosilanes is well‐established, and examples of similar oxidation at Si have been reported involving hydrolysis of PSiP‐supported complexes in the absence of O 2 (Figure , K – L ) , . Lastly, an intriguing related example of oxidation at Si was reported by Puddephatt and co‐workers for a Pt II ‐dimethyl complex supported by bis(2‐pyridyl)‐dimethylsilane (bps). Oxidation of (bps)PtMe 2 with oxygen/MeOH occurs with cleavage of a Me–Si bond to afford a Pt IV ‐siloxy species (Figure , I ).…”

Section: Resultsmentioning

confidence: 68%

“…Moreover, the observation of multiple unidentified products in this reaction further complicates the mechanistic possibilities . By comparison, Puddephatt and co‐workers propose that the siloxane I (Figure ) is formed by a pathway involving initial formation of a hydroperoxo Pt IV cation with a methoxide anion, which reacts rapidly with a second molecule of (bps)PtMe 2 to form a cationic Pt IV ‐hydroxo complex with a methoxide anion. Nucleophilic attack of the methoxide group at Si and methyl group transfer to Pt, followed by the displacement of the methoxy group from Si by the Pt‐OH group affords the product I with elimination of methanol.…”

Section: Resultsmentioning

confidence: 99%

Activation of Molecular Hydrogen and Oxygen by PSiP Complexes of Cobalt

et al. 2018

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The syntheses of CoII halide complexes supported by κ3‐(2‐Cy2PC6H4)2SiMe (Cy‐PSiP) ligation are detailed. Reduction of (Cy‐PSiP)Co(PMe3)I could be achieved under mild conditions using magnesium metal to generate the CoI complex (Cy‐PSiP)Co(PMe3)N2 in high yield. When this reaction was carried out under an atmosphere of CO, (Cy‐PSiP)Co(CO)2 was obtained. Unlike the facile reduction of CoII to CoI, attempts to access CoIII species supported by Cy‐PSiP ligation proved challenging. Attempted oxidative addition reactions involving (Cy‐PSiP)Co(PMe3)N2 were generally unsuccessful, with the sole exception of H2, which reacted to afford the dihydride complex (Cy‐PSiP)Co(PMe3)(H)2. The dihydride complex undergoes Co‐H site exchange in solution and readily eliminates H2. The CoI precursor (Cy‐PSiP)Co(PMe3)N2 is a competent precatalyst for the hydrogenation of terminal alkenes. Exposure of (Cy‐PSiP)CoI to O2 gas under anhydrous conditions led to rapid ligand oxidation at Si and P, with no evidence observed at low temperature for a CoIII superoxo or peroxo intermediate. Exclusive oxidation at Si to afford a CoII‐siloxy complex was observed upon treatment of (Cy‐PSiP)CoI with one equiv. Me3NO. While this siloxy complex did not react further with O2, treatment with a second equiv. of Me3NO led to subsequent oxidation involving one phosphino donor. This observation supports the notion that in the ligand oxidation reactivity observed with O2, the O atoms incorporated at both Si and P are likely derived from the same O2 molecule.

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Easy oxidatively induced silicon–carbon bond activation in organoplatinum chemistry

Cited by 14 publications

References 21 publications

Methyl Complexes of the Transition Metals

Methyl Complexes of the Transition Metals

Reactions of Pd and Pt Complexes with Molecular Oxygen

Activation of Molecular Hydrogen and Oxygen by PSiP Complexes of Cobalt

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