Metal-Ligand Cooperation as Key in Formation of Dearomatized NiII-H Pincer Complexes and in Their Reactivity toward CO and CO2

Dror Oren, Yael Diskin-Posner, Liat Avram, Moran Feller, David Milstein

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The unique synthesis and reactivity of [(RPNP∗)NiH] complexes (1a,b), based on metal-ligand cooperation (MLC), are presented (RPNP∗ = deprotonated PNP ligand, R = iPr, tBu). Unexpectedly, the dearomatized complexes 1a,b were obtained by reduction of the dicationic complexes [(RPNP)Ni(MeCN)](BF4)2 with sodium amalgam or by reaction of the free ligand with Ni0(COD)2. Complex 1b reacts with CO via MLC, to give a rare case of a distorted-octahedral PNP-based pincer complex, the Ni(0) complex 3b. Complexes 1a,b also react with CO2 via MLC to form a rare example of η1 binding of CO2 to nickel, complexes 4a,b. An unusual CO2 cleavage process by complex 4b, involving C-O and C-P cleavage and C-C bond formation, led to the Ni-CO complex 3b and to the new complex [(PiPr2NC2O2)Ni(P(O)iPr2)] (5b). All complexes have been fully characterized by NMR and X-ray crystallography.

Original languageEnglish
Pages (from-to)2217-2221
Number of pages5
JournalOrganometallics
Volume37
Issue number14
DOIs
Publication statusPublished - Jul 23 2018

Fingerprint

Carbon Monoxide
reactivity
Metals
Ligands
ligands
metals
cleavage
mercury amalgams
Mercury amalgams
crack opening displacement
X ray crystallography
Nickel
crystallography
Sodium
Nuclear magnetic resonance
sodium
nickel
nuclear magnetic resonance
synthesis
x rays

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Metal-Ligand Cooperation as Key in Formation of Dearomatized NiII-H Pincer Complexes and in Their Reactivity toward CO and CO2 . / Oren, Dror; Diskin-Posner, Yael; Avram, Liat; Feller, Moran; Milstein, David.

In: Organometallics, Vol. 37, No. 14, 23.07.2018, p. 2217-2221.

Research output: Contribution to journalArticle

Oren, Dror ; Diskin-Posner, Yael ; Avram, Liat ; Feller, Moran ; Milstein, David. / Metal-Ligand Cooperation as Key in Formation of Dearomatized NiII-H Pincer Complexes and in Their Reactivity toward CO and CO2 In: Organometallics. 2018 ; Vol. 37, No. 14. pp. 2217-2221.
@article{2bb6b05984904fceb600425766f58634,
title = "Metal-Ligand Cooperation as Key in Formation of Dearomatized NiII-H Pincer Complexes and in Their Reactivity toward CO and CO2",
abstract = "The unique synthesis and reactivity of [(RPNP∗)NiH] complexes (1a,b), based on metal-ligand cooperation (MLC), are presented (RPNP∗ = deprotonated PNP ligand, R = iPr, tBu). Unexpectedly, the dearomatized complexes 1a,b were obtained by reduction of the dicationic complexes [(RPNP)Ni(MeCN)](BF4)2 with sodium amalgam or by reaction of the free ligand with Ni0(COD)2. Complex 1b reacts with CO via MLC, to give a rare case of a distorted-octahedral PNP-based pincer complex, the Ni(0) complex 3b. Complexes 1a,b also react with CO2 via MLC to form a rare example of η1 binding of CO2 to nickel, complexes 4a,b. An unusual CO2 cleavage process by complex 4b, involving C-O and C-P cleavage and C-C bond formation, led to the Ni-CO complex 3b and to the new complex [(PiPr2NC2O2)Ni(P(O)iPr2)] (5b). All complexes have been fully characterized by NMR and X-ray crystallography.",
author = "Dror Oren and Yael Diskin-Posner and Liat Avram and Moran Feller and David Milstein",
year = "2018",
month = "7",
day = "23",
doi = "10.1021/acs.organomet.8b00160",
language = "English",
volume = "37",
pages = "2217--2221",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "14",

}

TY - JOUR

T1 - Metal-Ligand Cooperation as Key in Formation of Dearomatized NiII-H Pincer Complexes and in Their Reactivity toward CO and CO2

AU - Oren, Dror

AU - Diskin-Posner, Yael

AU - Avram, Liat

AU - Feller, Moran

AU - Milstein, David

PY - 2018/7/23

Y1 - 2018/7/23

N2 - The unique synthesis and reactivity of [(RPNP∗)NiH] complexes (1a,b), based on metal-ligand cooperation (MLC), are presented (RPNP∗ = deprotonated PNP ligand, R = iPr, tBu). Unexpectedly, the dearomatized complexes 1a,b were obtained by reduction of the dicationic complexes [(RPNP)Ni(MeCN)](BF4)2 with sodium amalgam or by reaction of the free ligand with Ni0(COD)2. Complex 1b reacts with CO via MLC, to give a rare case of a distorted-octahedral PNP-based pincer complex, the Ni(0) complex 3b. Complexes 1a,b also react with CO2 via MLC to form a rare example of η1 binding of CO2 to nickel, complexes 4a,b. An unusual CO2 cleavage process by complex 4b, involving C-O and C-P cleavage and C-C bond formation, led to the Ni-CO complex 3b and to the new complex [(PiPr2NC2O2)Ni(P(O)iPr2)] (5b). All complexes have been fully characterized by NMR and X-ray crystallography.

AB - The unique synthesis and reactivity of [(RPNP∗)NiH] complexes (1a,b), based on metal-ligand cooperation (MLC), are presented (RPNP∗ = deprotonated PNP ligand, R = iPr, tBu). Unexpectedly, the dearomatized complexes 1a,b were obtained by reduction of the dicationic complexes [(RPNP)Ni(MeCN)](BF4)2 with sodium amalgam or by reaction of the free ligand with Ni0(COD)2. Complex 1b reacts with CO via MLC, to give a rare case of a distorted-octahedral PNP-based pincer complex, the Ni(0) complex 3b. Complexes 1a,b also react with CO2 via MLC to form a rare example of η1 binding of CO2 to nickel, complexes 4a,b. An unusual CO2 cleavage process by complex 4b, involving C-O and C-P cleavage and C-C bond formation, led to the Ni-CO complex 3b and to the new complex [(PiPr2NC2O2)Ni(P(O)iPr2)] (5b). All complexes have been fully characterized by NMR and X-ray crystallography.

UR - http://www.scopus.com/inward/record.url?scp=85050491960&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85050491960&partnerID=8YFLogxK

U2 - 10.1021/acs.organomet.8b00160

DO - 10.1021/acs.organomet.8b00160

M3 - Article

VL - 37

SP - 2217

EP - 2221

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 14

ER -