Photochemical reactions of (η-C5H5)Fe(CO)2SiMe2R (R = Me, Ph) with ArCHO (Ar = C6H5, p-OCH3C6H4)

Vargas, Roy M.; Hossain, M. Mahmun

doi:10.1016/s0020-1693(00)82916-3

Cited by 5 publications

(3 citation statements)

References 7 publications

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“…We propose the silyl intermediate A as the active species. Insertion of a CO bond into the Fe–Si bond of B forms a silyloxyalkyl intermediate C . Reaction of C with hydrosilane gives the product and regenerates A .…”

Section: Results and Discussionmentioning

confidence: 99%

Preparation, Characterization, and Catalytic Reactions of NCN Pincer Iron Complexes Containing Stannyl, Silyl, Methyl, and Phenyl Ligands

et al. 2015

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Preparation and reactivity of chiral and achiral NCN pincer Fe complexes containing bis(oxazolinyl)phenyl (abbreviated as phebox) ligands with SnMe 3 , SiMe 3 , Me, and Ph ligands were investigated. Irradiation of (phebox)SnMe 3 (2) with 1 equiv of Fe(CO) 5 led to oxidative addition to give NCN pincer stannyl complex (phebox)Fe(CO) 2 (SnMe 3 ) (3). Similarly, oxidative addition of (phebox)SiMe 3 (4) with Fe(CO) 5 resulted in the formation of silyl complex (phebox)Fe(CO) 2 SiMe 3 (5). Me and Ph complexes (phebox)Fe(CO) 2 R (7, R = Me; 8, R = Ph) were synthesized by transmetalation of the bromide complex (phebox)Fe(CO) 2 Br (1) with ZnMe 2 and ZnPh 2 , respectively. These phebox Fe complexes served as catalysts for hydrosilylation of a ketone and C−H silylation of N-methylindole.

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Section: Results and Discussionmentioning

confidence: 99%

Preparation, Characterization, and Catalytic Reactions of NCN Pincer Iron Complexes Containing Stannyl, Silyl, Methyl, and Phenyl Ligands

et al. 2015

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“…In such a context, so-called “anomalous” insertions of CO 2 exhibiting a reversed regiochemical preference are appealing reaction targets (Figure ), since an electronegative metal and electropositive silicon might be tuned to reveal a M δ− –Si δ+ façade for substrate activation. Migratory insertions of CO 2 into metal–silicon bonds are known, yet all reported examples of well-defined insertions of CO 2 follow the normal pathway in spite of the well-known oxophilicity of silicon and the propensity of aldehydes and ketones to insert into M–Si in anomalous fashion. , In this contribution, we show a pathway for CO 2 scission and further elaboration initiated by anomalous insertion into a Rh–Si bond; we also explore the electronic characteristics that engender such reactivity.…”

Section: Introductionmentioning

confidence: 93%

Cooperative CO₂ Scission by Anomalous Insertion into a Rh–Si Bond

et al. 2019

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Pincer-type [P 2 Si]Rh complexes featuring a rhodium−silicon bond are shown to facilitate well-defined stoichiometric reductions of CO 2 with Si−O bond formation by two different pathways: (a) hydride transfer to CO 2 followed by formate migration to silicon, or (b) complete scission of the CO bond at the Rh−Si unit to afford a product with siloxide and carbonyl ligands. A combined experimental and computational study shows that the latter process occurs by anomalous insertion of CO 2 into the polarized Rh δ− −Si δ+ bond, a finding that is confirmed by extending the reactivity to an unchelated system. The siloxide carbonyl product can be further elaborated by reaction with water or pinacolborane to give structurally distinct CO 2 reduction products. Taken together, these results demonstrate how metal/main-group bonds can be tuned to direct migratory insertion reactivity.

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“…4,5-Bis(4-methoxyphenyl)-2,7-dimethyl-2,7-diphenyl-3,6-dioxa-2,7-disilaoctane (meso and DL, 4a). 24 Colorless oil (29.1 mg, 75% yield); 1 H NMR (500 MHz, CDCl 3 ): 7.46−6.65 (m, 18H meso and 18H DL), 4.64 (s, 2H, meso), 4.48 (s, 2H, DL), 3.83 (s, 6H, DL), 3.76 (s, 6H, meso), 0.40 (s, 6H, meso), 0.20 (s, 6H, meso), 0.03 (s, 6H, DL), −0.04 (s, 6H, DL); 13 4,5-Bis(4-fluorophenyl)-2,7-dimethyl-2,7-diphenyl-3,6-dioxa-2,7disilaoctane (meso and DL, 5a). 23 Colorless oil (22.2 mg, 62% yield); 1 H NMR (500 MHz, CDCl 3 ): 7.41−6.79 (m, 18H meso and 18H DL), 4.64 (s, 2H, meso), 4.44 (s, 2H, DL), 0.21 (s, 6H, meso), 0.15 (s, 6H, meso), 0.02 (s, 6H, DL), −0.04 (s, 6H, DL); 13 2,7-Dimethyl-4,5-di(naphthalen-2-yl)-2,7-diphenyl-3,6-dioxa-2,7-disilaoctane (meso and DL, 6a).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Reaction of Aromatic Carbonyl Compounds with Silylborane Catalyzed by Au Nanoparticles: Silylative Pinacol-type Reductive Dimerization via a Radical Pathway

2018

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Aromatic aldehydes and acetophenones undergo silylative pinacol-type reductive dimerization in their reaction with silylborane pinB-SiMe 2 Ph (pin: pinacolato) catalyzed by supported Au nanoparticles on TiO 2 . It is proposed that after initial activation of silylborane by Au nanoparticles and addition to the carbonyl functionality of an aromatic aldehyde or ketone, an aryl silyloxy radical is generated from the collapse of the intermediate adduct, which then dimerizes through a chain process. The silyloxy radical was almost quantitatively trapped in the presence of TEMPO.

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Photochemical reactions of (η-C5H5)Fe(CO)2SiMe2R (R = Me, Ph) with ArCHO (Ar = C6H5, p-OCH3C6H4)

Cited by 5 publications

References 7 publications

Preparation, Characterization, and Catalytic Reactions of NCN Pincer Iron Complexes Containing Stannyl, Silyl, Methyl, and Phenyl Ligands

Preparation, Characterization, and Catalytic Reactions of NCN Pincer Iron Complexes Containing Stannyl, Silyl, Methyl, and Phenyl Ligands

Cooperative CO₂ Scission by Anomalous Insertion into a Rh–Si Bond

Reaction of Aromatic Carbonyl Compounds with Silylborane Catalyzed by Au Nanoparticles: Silylative Pinacol-type Reductive Dimerization via a Radical Pathway

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Photochemical reactions of (η-C5H5)Fe(CO)2SiMe2R (R = Me, Ph) with ArCHO (Ar = C6H5, p-OCH3C6H4)

Cited by 5 publications

References 7 publications

Preparation, Characterization, and Catalytic Reactions of NCN Pincer Iron Complexes Containing Stannyl, Silyl, Methyl, and Phenyl Ligands

Preparation, Characterization, and Catalytic Reactions of NCN Pincer Iron Complexes Containing Stannyl, Silyl, Methyl, and Phenyl Ligands

Cooperative CO2 Scission by Anomalous Insertion into a Rh–Si Bond

Reaction of Aromatic Carbonyl Compounds with Silylborane Catalyzed by Au Nanoparticles: Silylative Pinacol-type Reductive Dimerization via a Radical Pathway

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Cooperative CO₂ Scission by Anomalous Insertion into a Rh–Si Bond