[(tBu2PCH2SiMe2) 2N]Rhi? Rapidly reversible H-C(sp3) and H-C(sp2) bond cleavage by rhodium(I)

Alexander Y. Verat; Maren Pink; Hongjun Fan; John Tomaszewski; Kenneth G. Caulton

doi:10.1021/om701165n

[(^tBu₂PCH₂SiMe₂) ₂N]Rhⁱ? Rapidly reversible H-C(sp³) and H-C(sp²) bond cleavage by rhodium(I)

Alexander Y. Verat
, Maren Pink
, Hongjun Fan
, John Tomaszewski
, Kenneth G. Caulton

Department of Pathology and Anatomical Sciences

Indiana University Bloomington

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

57 Scopus citations

Abstract

The product of the reaction of (^tBu₂PCH ₂SiMe₂)₂N^- (MgCl⁺ salt) with [RhCl(cyclooctene)₂]₂ is a Rh^III complex where one ^tBu methyl C-H bond has oxidatively added to Rh: (PNP*)RhH. This is in rapid exchange among all 9 × 4 C-H bonds of the four ^tBu groups. (PNP*)RhH undergoes oxidative addition equilibrium with the C-H bonds of benzene at ∼10³ s^-1 at 25°C and oxidatively adds the ring C-H of other arenes. (PNP*)RhH forms η²-olefin complexes with several olefins and dehydrogenates allylic C-H bonds to form (PNP)Rh(H)₂.

Original language	English
Pages (from-to)	166-168
Number of pages	3
Journal	Organometallics
Volume	27
Issue number	2
DOIs	https://doi.org/10.1021/om701165n
State	Published - Jan 28 2008

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title = "[(tBu2PCH2SiMe2) 2N]Rhi? Rapidly reversible H-C(sp3) and H-C(sp2) bond cleavage by rhodium(I)",

abstract = "The product of the reaction of (tBu2PCH 2SiMe2)2N- (MgCl+ salt) with [RhCl(cyclooctene)2]2 is a RhIII complex where one tBu methyl C-H bond has oxidatively added to Rh: (PNP*)RhH. This is in rapid exchange among all 9 × 4 C-H bonds of the four tBu groups. (PNP*)RhH undergoes oxidative addition equilibrium with the C-H bonds of benzene at ∼103 s-1 at 25°C and oxidatively adds the ring C-H of other arenes. (PNP*)RhH forms η2-olefin complexes with several olefins and dehydrogenates allylic C-H bonds to form (PNP)Rh(H)2.",

author = "Verat, \{Alexander Y.\} and Maren Pink and Hongjun Fan and John Tomaszewski and Caulton, \{Kenneth G.\}",

year = "2008",

month = jan,

day = "28",

doi = "10.1021/om701165n",

language = "English",

volume = "27",

pages = "166--168",

journal = "Organometallics",

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TY - JOUR

T1 - [(tBu2PCH2SiMe2) 2N]Rhi? Rapidly reversible H-C(sp3) and H-C(sp2) bond cleavage by rhodium(I)

AU - Verat, Alexander Y.

AU - Pink, Maren

AU - Fan, Hongjun

AU - Tomaszewski, John

AU - Caulton, Kenneth G.

PY - 2008/1/28

Y1 - 2008/1/28

N2 - The product of the reaction of (tBu2PCH 2SiMe2)2N- (MgCl+ salt) with [RhCl(cyclooctene)2]2 is a RhIII complex where one tBu methyl C-H bond has oxidatively added to Rh: (PNP*)RhH. This is in rapid exchange among all 9 × 4 C-H bonds of the four tBu groups. (PNP*)RhH undergoes oxidative addition equilibrium with the C-H bonds of benzene at ∼103 s-1 at 25°C and oxidatively adds the ring C-H of other arenes. (PNP*)RhH forms η2-olefin complexes with several olefins and dehydrogenates allylic C-H bonds to form (PNP)Rh(H)2.

AB - The product of the reaction of (tBu2PCH 2SiMe2)2N- (MgCl+ salt) with [RhCl(cyclooctene)2]2 is a RhIII complex where one tBu methyl C-H bond has oxidatively added to Rh: (PNP*)RhH. This is in rapid exchange among all 9 × 4 C-H bonds of the four tBu groups. (PNP*)RhH undergoes oxidative addition equilibrium with the C-H bonds of benzene at ∼103 s-1 at 25°C and oxidatively adds the ring C-H of other arenes. (PNP*)RhH forms η2-olefin complexes with several olefins and dehydrogenates allylic C-H bonds to form (PNP)Rh(H)2.

UR - https://www.scopus.com/pages/publications/38949083488

U2 - 10.1021/om701165n

DO - 10.1021/om701165n

M3 - Article

AN - SCOPUS:38949083488

SN - 0276-7333

VL - 27

SP - 166

EP - 168

JO - Organometallics

JF - Organometallics

IS - 2

ER -

[(^tBu₂PCH₂SiMe₂) ₂N]Rhⁱ? Rapidly reversible H-C(sp³) and H-C(sp²) bond cleavage by rhodium(I)

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