A transient vanadium(III) neopentylidene complex. Redox chemistry and reactivity of the V=CH tBu functionality

Uriah J. Kilgore; Caitlin A. Sengelaub; Hongjun Fan; John Tomaszewski; Jonathan A. Karty; Mu Hyun Baik; Daniel J. Mindiola

doi:10.1021/om800800g

A transient vanadium(III) neopentylidene complex. Redox chemistry and reactivity of the V=CH ^tBu functionality

Uriah J. Kilgore
, Caitlin A. Sengelaub
, Hongjun Fan
, John Tomaszewski
, Jonathan A. Karty
, Mu Hyun Baik
, Daniel J. Mindiola

Department of Pathology and Anatomical Sciences

Indiana University Bloomington
Yale University

Research output: Contribution to journal › Article › peer-review

57 Scopus citations

Abstract

The vanadium(III) bis(neopentyl) complex (PNP)V(CH ₂ ^tBu) ₂ (PNP = N[4-Me-2-(P ⁱPr ₂)C ₆H ₃] ₂ ^-), a complex readily prepared from alkylation of (PNP)VCl ₂ with 2 equiv of LiCH ₂ ^tBu, serves as a precursor to the transient vanadium(III) alkylidene complex "(PNP)V=CH ^tBu". Two-electron oxidation of the intermediate [(PNP)V=CH ^tBu] with chalcogen sources results in formation of the vanadium(V) chalcogenide series (PNP)V=CH ^tBu(X) (X = O, S, Se, Te). This family of chalcogenide - alkylidenes has been studied via ⁵¹V NMR spectroscopy in combination with DFT computational methods. The redox chemistry of [(PNP)V=CH ^tBu] and the reactivity of the alkylidene ligand are explored with the substrates N ₃SiMe ₃, N≡C ^tBu, N ₂, and azobenzene. It was discovered that N=N cleavage of the last substrate can be achieved without oxidation of the metal.

Original language	English
Pages (from-to)	843-852
Number of pages	10
Journal	Organometallics
Volume	28
Issue number	3
DOIs	https://doi.org/10.1021/om800800g
State	Published - Feb 9 2009

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@article{f4ab92acd05546208fe7e9577ebc54b8,

title = "A transient vanadium(III) neopentylidene complex. Redox chemistry and reactivity of the V=CH tBu functionality",

abstract = "The vanadium(III) bis(neopentyl) complex (PNP)V(CH 2 tBu) 2 (PNP = N[4-Me-2-(P iPr 2)C 6H 3] 2 -), a complex readily prepared from alkylation of (PNP)VCl 2 with 2 equiv of LiCH 2 tBu, serves as a precursor to the transient vanadium(III) alkylidene complex {"}(PNP)V=CH tBu{"}. Two-electron oxidation of the intermediate [(PNP)V=CH tBu] with chalcogen sources results in formation of the vanadium(V) chalcogenide series (PNP)V=CH tBu(X) (X = O, S, Se, Te). This family of chalcogenide - alkylidenes has been studied via 51V NMR spectroscopy in combination with DFT computational methods. The redox chemistry of [(PNP)V=CH tBu] and the reactivity of the alkylidene ligand are explored with the substrates N 3SiMe 3, N≡C tBu, N 2, and azobenzene. It was discovered that N=N cleavage of the last substrate can be achieved without oxidation of the metal.",

author = "Kilgore, \{Uriah J.\} and Sengelaub, \{Caitlin A.\} and Hongjun Fan and John Tomaszewski and Karty, \{Jonathan A.\} and Baik, \{Mu Hyun\} and Mindiola, \{Daniel J.\}",

year = "2009",

month = feb,

day = "9",

doi = "10.1021/om800800g",

language = "English",

volume = "28",

pages = "843--852",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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T1 - A transient vanadium(III) neopentylidene complex. Redox chemistry and reactivity of the V=CH tBu functionality

AU - Kilgore, Uriah J.

AU - Sengelaub, Caitlin A.

AU - Fan, Hongjun

AU - Tomaszewski, John

AU - Karty, Jonathan A.

AU - Baik, Mu Hyun

AU - Mindiola, Daniel J.

PY - 2009/2/9

Y1 - 2009/2/9

N2 - The vanadium(III) bis(neopentyl) complex (PNP)V(CH 2 tBu) 2 (PNP = N[4-Me-2-(P iPr 2)C 6H 3] 2 -), a complex readily prepared from alkylation of (PNP)VCl 2 with 2 equiv of LiCH 2 tBu, serves as a precursor to the transient vanadium(III) alkylidene complex "(PNP)V=CH tBu". Two-electron oxidation of the intermediate [(PNP)V=CH tBu] with chalcogen sources results in formation of the vanadium(V) chalcogenide series (PNP)V=CH tBu(X) (X = O, S, Se, Te). This family of chalcogenide - alkylidenes has been studied via 51V NMR spectroscopy in combination with DFT computational methods. The redox chemistry of [(PNP)V=CH tBu] and the reactivity of the alkylidene ligand are explored with the substrates N 3SiMe 3, N≡C tBu, N 2, and azobenzene. It was discovered that N=N cleavage of the last substrate can be achieved without oxidation of the metal.

AB - The vanadium(III) bis(neopentyl) complex (PNP)V(CH 2 tBu) 2 (PNP = N[4-Me-2-(P iPr 2)C 6H 3] 2 -), a complex readily prepared from alkylation of (PNP)VCl 2 with 2 equiv of LiCH 2 tBu, serves as a precursor to the transient vanadium(III) alkylidene complex "(PNP)V=CH tBu". Two-electron oxidation of the intermediate [(PNP)V=CH tBu] with chalcogen sources results in formation of the vanadium(V) chalcogenide series (PNP)V=CH tBu(X) (X = O, S, Se, Te). This family of chalcogenide - alkylidenes has been studied via 51V NMR spectroscopy in combination with DFT computational methods. The redox chemistry of [(PNP)V=CH tBu] and the reactivity of the alkylidene ligand are explored with the substrates N 3SiMe 3, N≡C tBu, N 2, and azobenzene. It was discovered that N=N cleavage of the last substrate can be achieved without oxidation of the metal.

UR - https://www.scopus.com/pages/publications/61849137313

U2 - 10.1021/om800800g

DO - 10.1021/om800800g

M3 - Article

AN - SCOPUS:61849137313

SN - 0276-7333

VL - 28

SP - 843

EP - 852

JO - Organometallics

JF - Organometallics

IS - 3

ER -

A transient vanadium(III) neopentylidene complex. Redox chemistry and reactivity of the V=CH ^tBu functionality

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