Chromium(II) Pincer Complexes with Dearomatized PNP and PNC Ligands: A Comparative Study of Their Catalytic Ethylene Oligomerization Activity

Thomas Simler; Pierre Braunstein; Andreas A. Danopoulos

doi:10.1021/acs.organomet.6b00685

Chromium(II) Pincer Complexes with Dearomatized PNP and PNC Ligands: A Comparative Study of Their Catalytic Ethylene Oligomerization Activity

Thomas Simler
, Pierre Braunstein
, Andreas A. Danopoulos

Institut de Chimie de Strasbourg
Université de Strasbourg

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

Abstract

Monodeprotonation of the 2,6-bis(di-tert-butylphosphinomethyl) pyridine (^tBuPN^tBuP) at the α-lutidinyl-CH₂ position with 1 equiv of KCH₂C₆H₅ and concomitant dearomatization of the heterocycle afforded K(^tBuP∗N_a^tBuP) (^tBuP∗= di-tert-butyl vinylic P donor, ^tBuP = PtBu₂, N_a = anionic amido N donor); its transmetalation with [CrCl₂(THF)₂] afforded the Cr^II complex [Cr(^tBuP∗N_a^tBuP)Cl] (A). The X-ray diffraction analysis of A established a slightly distorted square-planar coordination geometry at the metal center and confirmed retention of the dearomatized coordinated ligand. The catalytic activity of A in ethylene oligomerization was studied and compared with that of the related Cr^II complexes [Cr(^tBuP∗N_aC^NHC)Cl] (B) and [Cr{Cr(^tBuP∗N_a^tBuP∗)Cl}₂] (C) previously reported [ Chem. Commun., 2015, 51, 10699 and Dalton Trans., 2016, 45, 2800, respectively].

Original language	English
Pages (from-to)	4044-4049
Number of pages	6
Journal	Organometallics
Volume	35
Issue number	24
DOIs	https://doi.org/10.1021/acs.organomet.6b00685
Publication status	Published - 27 Dec 2016
Externally published	Yes

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@article{78ff51dc254e40e29d07deaa014a1b7e,

title = "Chromium(II) Pincer Complexes with Dearomatized PNP and PNC Ligands: A Comparative Study of Their Catalytic Ethylene Oligomerization Activity",

abstract = "Monodeprotonation of the 2,6-bis(di-tert-butylphosphinomethyl) pyridine (tBuPNtBuP) at the α-lutidinyl-CH2 position with 1 equiv of KCH2C6H5 and concomitant dearomatization of the heterocycle afforded K(tBuP∗NatBuP) (tBuP∗= di-tert-butyl vinylic P donor, tBuP = PtBu2, Na = anionic amido N donor); its transmetalation with [CrCl2(THF)2] afforded the CrII complex [Cr(tBuP∗NatBuP)Cl] (A). The X-ray diffraction analysis of A established a slightly distorted square-planar coordination geometry at the metal center and confirmed retention of the dearomatized coordinated ligand. The catalytic activity of A in ethylene oligomerization was studied and compared with that of the related CrII complexes [Cr(tBuP∗NaCNHC)Cl] (B) and [Cr\{Cr(tBuP∗NatBuP∗)Cl\}2] (C) previously reported [ Chem. Commun., 2015, 51, 10699 and Dalton Trans., 2016, 45, 2800, respectively].",

author = "Thomas Simler and Pierre Braunstein and Danopoulos, \{Andreas A.\}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = dec,

day = "27",

doi = "10.1021/acs.organomet.6b00685",

language = "English",

volume = "35",

pages = "4044--4049",

journal = "Organometallics",

issn = "0276-7333",

number = "24",

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TY - JOUR

T1 - Chromium(II) Pincer Complexes with Dearomatized PNP and PNC Ligands

T2 - A Comparative Study of Their Catalytic Ethylene Oligomerization Activity

AU - Simler, Thomas

AU - Braunstein, Pierre

AU - Danopoulos, Andreas A.

PY - 2016/12/27

Y1 - 2016/12/27

N2 - Monodeprotonation of the 2,6-bis(di-tert-butylphosphinomethyl) pyridine (tBuPNtBuP) at the α-lutidinyl-CH2 position with 1 equiv of KCH2C6H5 and concomitant dearomatization of the heterocycle afforded K(tBuP∗NatBuP) (tBuP∗= di-tert-butyl vinylic P donor, tBuP = PtBu2, Na = anionic amido N donor); its transmetalation with [CrCl2(THF)2] afforded the CrII complex [Cr(tBuP∗NatBuP)Cl] (A). The X-ray diffraction analysis of A established a slightly distorted square-planar coordination geometry at the metal center and confirmed retention of the dearomatized coordinated ligand. The catalytic activity of A in ethylene oligomerization was studied and compared with that of the related CrII complexes [Cr(tBuP∗NaCNHC)Cl] (B) and [Cr{Cr(tBuP∗NatBuP∗)Cl}2] (C) previously reported [ Chem. Commun., 2015, 51, 10699 and Dalton Trans., 2016, 45, 2800, respectively].

AB - Monodeprotonation of the 2,6-bis(di-tert-butylphosphinomethyl) pyridine (tBuPNtBuP) at the α-lutidinyl-CH2 position with 1 equiv of KCH2C6H5 and concomitant dearomatization of the heterocycle afforded K(tBuP∗NatBuP) (tBuP∗= di-tert-butyl vinylic P donor, tBuP = PtBu2, Na = anionic amido N donor); its transmetalation with [CrCl2(THF)2] afforded the CrII complex [Cr(tBuP∗NatBuP)Cl] (A). The X-ray diffraction analysis of A established a slightly distorted square-planar coordination geometry at the metal center and confirmed retention of the dearomatized coordinated ligand. The catalytic activity of A in ethylene oligomerization was studied and compared with that of the related CrII complexes [Cr(tBuP∗NaCNHC)Cl] (B) and [Cr{Cr(tBuP∗NatBuP∗)Cl}2] (C) previously reported [ Chem. Commun., 2015, 51, 10699 and Dalton Trans., 2016, 45, 2800, respectively].

UR - https://www.scopus.com/pages/publications/85008417773

U2 - 10.1021/acs.organomet.6b00685

DO - 10.1021/acs.organomet.6b00685

M3 - Article

AN - SCOPUS:85008417773

SN - 0276-7333

VL - 35

SP - 4044

EP - 4049

JO - Organometallics

JF - Organometallics

IS - 24

ER -

Chromium(II) Pincer Complexes with Dearomatized PNP and PNC Ligands: A Comparative Study of Their Catalytic Ethylene Oligomerization Activity

Abstract

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