Synthesis and reactivity of a tungsten(0) anion stabilized by chelating tertiary amines. The oxidative addition and reductive elimination of a carbon-tin bond at tungsten

Buffin, Brian P.; Poss, Mitchell; Arif, Atta M.; Richmond, Thomas G.

doi:10.1021/ic00070a006

Cited by 27 publications

(14 citation statements)

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“…On the other hand, attempts to achieve intramolecular activation of aryl C−X or aryl C−H bonds in related saturated ligands Me 2 NCH 2 CH 2 N(Me)CH 2 R have been unsuccessful both at platinum(II) and at tungsten(0) . The greater tendency to form unsaturated metallacycles containing the CN group ( endo -cycles) than saturated metallacycles has been attributed to restricted rotation about the CN bond and to conjugation of the CN bond with the aryl ring …”

Section: Introductionmentioning

confidence: 99%

Activation of C−F and C−H Bonds by Platinum in Trifluorinated [C,N,N‘] Ligands. Crystal Structures of [PtFMe₂{Me₂NCH₂CH₂NHCH(CH₂COMe)(2,4-C₆H₂F₂)}] and [PtMe{Me₂NCH₂CH₂NCH(2,3,4-C₆HF₃)}]

Lopez¹,

Crespo²,

Font-Bardı́a³

et al. 1997

Organometallics

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Trifluorinated ligands Me2NCH2CH2NCHR (R = 2,4,6-C6H2F3 (2a), 2,3,6-C6H2F3 (2b)) react with [Pt2Me4(μ-SMe2)2] (1) to yield the [C,N,N‘] saturated cyclometalated platinum(IV) compounds [PtFMe2{Me2NCH2CH2NHCH(CH2COMe)(C6H2F2)}] (4) arising from CF bond activation followed by acetone addition on the iminic bond of the coordinated ligand. The reactions of the platinum substrate with trifluorinated ligands Me2NCH2CH2NCHR (R = 2,3,4-C6H2F3 (2c), 2,4,5-C6H2F3 (2d), 3,4,5-C6H2F3 (2e)) containing only one or no fluorine atom in the ortho positions yield the [C,N,N‘] cyclometalated platinum(II) compounds [PtMe(Me2NCH2CH2NCHC6HF3)] (5) by ortho metalation with loss of methane. Compounds 5 react with methyl iodide to yield the [C,N,N‘] unsaturated cyclometalated platinum(IV) compounds [PtIMe2(Me2NCH2CH2NCHC6HF3)] (6) and with triphenylphosphine to produce the displacement of the NMe2 moiety and the formation of [C,N] cyclometalated compounds [PtMe(PPh3)(Me2NCH2CH2NCHC6HF3)] (7c). When there is a fluorine atom adjacent to platinum (F5), the displacement of both nitrogen donor atoms takes place upon reaction with PPh3 to yield the compounds [PtMe(PPh3)2(Me2NCH2CH2NCHC6HF3)] (7d,e). All compounds were characterized by elemental analyses and NMR spectroscopy, and [PtFMe2{Me2NCH2CH2NHCH(CH2COMe)(2,4-C6H2F2)}] (4a) and [PtMe{Me2NCH2CH2NCH(2,3,4-C6HF3)}] (5c) were characterized crystallographically.

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Section: Introductionmentioning

confidence: 99%

Activation of C−F and C−H Bonds by Platinum in Trifluorinated [C,N,N‘] Ligands. Crystal Structures of [PtFMe₂{Me₂NCH₂CH₂NHCH(CH₂COMe)(2,4-C₆H₂F₂)}] and [PtMe{Me₂NCH₂CH₂NCH(2,3,4-C₆HF₃)}]

Lopez¹,

Crespo²,

Font-Bardı́a³

et al. 1997

Organometallics

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“…Due to our inability to isolate this alkyltungsten(II) intermediate in crystalline form, further studies focused on more thermally stable aryltungsten(II) species ( 37) to facilitate analysis by X-ray crystallography. Using an analogous synthetic sequence, the complexes W-2 and W-3 were prepared by oxidative addition of the corresponding aryl iodides SM-2 and SM-3 to W(0) (39). W-3 was then treated with AgOTf to abstract the iodide, and further treatment with KOt-Bu/18-crown-6 deprotonated the amide.…”

mentioning

confidence: 99%

Low-Valent Tungsten Redox Catalysis Enables Controlled Isomerization and Carbonylative Functionalization of Alkenes

Jankins¹,

Bell²,

Qin³

et al. 2021

Preprint

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Tungsten catalysis has played an instrumental role in the history of organometallic chemistry, with electrophilic, fully oxidized W(VI) catalysts featuring prominently in olefin polymerization and metathesis reactions. Here, we report that the simple W(0) precatalyst, W(CO)<sub>6</sub>, catalyzes the isomerization and hydrocarbonylation of alkenes via a W(0)/W(II) redox couple. The 6- to 7-coordinate geometry changes associated with this redox process are key in allowing isomerization to take place over multiple positions and stop at a defined unactivated internal site that is primed for <i>in situ</i> functionalization. DFT studies and crystallographic characterization of multiple directing-group-bound W(II) model complexes illuminate potential intermediates of this redox cycle and showcase the capabilities of the 7-coordinate W(II) geometry to facilitate challenging alkene functionalizations.

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“…]. Although NMR spectroscopic evidence † (P•C, d P 452.4, d C 315.2; 1 J PC 117.7, 1 J PW 82.0 Hz) fully confirmed 4 the expected formation of the green h 2 -(4e 6 was treated with Bu t C•P for 3 h in toluene at room temp. it proved impossible to isolate it in crystalline form.…”

Section: An Unusual Series Of Reactions Involving An Intermediate 4e ...mentioning

confidence: 95%

Carbon monoxide–phosphaalkyne coupling and C–H activation of an N–Me group in the 4e-η2-phosphaalkyne complex [WF(C6H4CH2NMeCH2CH2 NMe2)(CO)(η2-PCBut)]. Crystal and molecular structure of [WF{CH2N(CH2Ph)CH2CH2NMe 2}(CO){η4-PCBut(CO)CBu tP}]

Benvenutti¹,

Hitchcock²,

Kiplinger³

et al. 1997

Chem. Commun.

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Synthesis and reactivity of a tungsten(0) anion stabilized by chelating tertiary amines. The oxidative addition and reductive elimination of a carbon-tin bond at tungsten

Cited by 27 publications

References 0 publications

Activation of C−F and C−H Bonds by Platinum in Trifluorinated [C,N,N‘] Ligands. Crystal Structures of [PtFMe₂{Me₂NCH₂CH₂NHCH(CH₂COMe)(2,4-C₆H₂F₂)}] and [PtMe{Me₂NCH₂CH₂NCH(2,3,4-C₆HF₃)}]

Activation of C−F and C−H Bonds by Platinum in Trifluorinated [C,N,N‘] Ligands. Crystal Structures of [PtFMe₂{Me₂NCH₂CH₂NHCH(CH₂COMe)(2,4-C₆H₂F₂)}] and [PtMe{Me₂NCH₂CH₂NCH(2,3,4-C₆HF₃)}]

Low-Valent Tungsten Redox Catalysis Enables Controlled Isomerization and Carbonylative Functionalization of Alkenes

Carbon monoxide–phosphaalkyne coupling and C–H activation of an N–Me group in the 4e-η2-phosphaalkyne complex [WF(C6H4CH2NMeCH2CH2 NMe2)(CO)(η2-PCBut)]. Crystal and molecular structure of [WF{CH2N(CH2Ph)CH2CH2NMe 2}(CO){η4-PCBut(CO)CBu tP}]

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Synthesis and reactivity of a tungsten(0) anion stabilized by chelating tertiary amines. The oxidative addition and reductive elimination of a carbon-tin bond at tungsten

Cited by 27 publications

References 0 publications

Activation of C−F and C−H Bonds by Platinum in Trifluorinated [C,N,N‘] Ligands. Crystal Structures of [PtFMe2{Me2NCH2CH2NHCH(CH2COMe)(2,4-C6H2F2)}] and [PtMe{Me2NCH2CH2NCH(2,3,4-C6HF3)}]

Activation of C−F and C−H Bonds by Platinum in Trifluorinated [C,N,N‘] Ligands. Crystal Structures of [PtFMe2{Me2NCH2CH2NHCH(CH2COMe)(2,4-C6H2F2)}] and [PtMe{Me2NCH2CH2NCH(2,3,4-C6HF3)}]

Low-Valent Tungsten Redox Catalysis Enables Controlled Isomerization and Carbonylative Functionalization of Alkenes

Carbon monoxide–phosphaalkyne coupling and C–H activation of an N–Me group in the 4e-η2-phosphaalkyne complex [WF(C6H4CH2NMeCH2CH2 NMe2)(CO)(η2-PCBut)]. Crystal and molecular structure of [WF{CH2N(CH2Ph)CH2CH2NMe 2}(CO){η4-PCBut(CO)CBu tP}]

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Activation of C−F and C−H Bonds by Platinum in Trifluorinated [C,N,N‘] Ligands. Crystal Structures of [PtFMe₂{Me₂NCH₂CH₂NHCH(CH₂COMe)(2,4-C₆H₂F₂)}] and [PtMe{Me₂NCH₂CH₂NCH(2,3,4-C₆HF₃)}]

Activation of C−F and C−H Bonds by Platinum in Trifluorinated [C,N,N‘] Ligands. Crystal Structures of [PtFMe₂{Me₂NCH₂CH₂NHCH(CH₂COMe)(2,4-C₆H₂F₂)}] and [PtMe{Me₂NCH₂CH₂NCH(2,3,4-C₆HF₃)}]