skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Heteroleptic Nickel Complexes of a Bulky Bis(carbene)borate Ligand

Abstract

Bis(carbene)borate ligand transfer to the nickel nitrosyl synthon Ni(NO)(PPh3)2Br provides the new nickel nitrosyl complex Ph2B(tBuIm)2Ni(NO)(PPh3). The solid state structure reveals a trigonal pyramidal nickel ion with a very long bond to the apical PPh3 ligand. The complex reversibly dissociates PPh3 in solution to afford three-coordinate Ph2B(tBuIm)2Ni(NO), with NMR data providing evidence for PPh3 binding at low temperatures. Ligand transfer to Ni(PMe3)2Cl2 provides the square planar complex, Ph2B(tBuIm)2Ni(PMe3)Cl, which shows no evidence for rearranging to the form a homoleptic complex with two bis(carbene)borate ligands. This complex is a suitable synthon for the [Ph2B(tBuIm)2Ni]+ fragment, as demonstrated by the synthesis of the π-allyl complex Ph2B(tBuIm)2Ni(η3-C7H7). The π-allyl complex reacts with O2 to provide benzaldehyde and an unstable complex that is tentatively identified as the nickel(II) hydroxide [Ph2B(tBuIm)2Ni(μ-OH)]2.

Authors:
 [1];  [2];  [2];  [2];  [2]
  1. Indiana Univ., Bloomington, IN (United States). Dept. of Chemistry; Loyola Univ. Chicago, Chicago, IL (United States). Dept. of Chemistry and Biochemistry
  2. Indiana Univ., Bloomington, IN (United States). Dept. of Chemistry
Publication Date:
Research Org.:
New Mexico State Univ., Las Cruces, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1471492
Alternate Identifier(s):
OSTI ID: 1636409
Grant/Contract Number:  
FG02-08ER15996
Resource Type:
Accepted Manuscript
Journal Name:
Polyhedron
Additional Journal Information:
Journal Volume: 156; Journal Issue: 1; Journal ID: ISSN 0277-5387
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Nickel complexes; nitrosyl ligands, NHC complexes, bidentate ligands; dioxygen reactivity

Citation Formats

Martinez, Jorge L., Lee, Wei-Tsung, Pink, Maren, Chen, Chun-Hsing, and Smith, Jeremy M.. Heteroleptic Nickel Complexes of a Bulky Bis(carbene)borate Ligand. United States: N. p., 2018. Web. https://doi.org/10.1016/j.poly.2018.09.026.
Martinez, Jorge L., Lee, Wei-Tsung, Pink, Maren, Chen, Chun-Hsing, & Smith, Jeremy M.. Heteroleptic Nickel Complexes of a Bulky Bis(carbene)borate Ligand. United States. https://doi.org/10.1016/j.poly.2018.09.026
Martinez, Jorge L., Lee, Wei-Tsung, Pink, Maren, Chen, Chun-Hsing, and Smith, Jeremy M.. Tue . "Heteroleptic Nickel Complexes of a Bulky Bis(carbene)borate Ligand". United States. https://doi.org/10.1016/j.poly.2018.09.026. https://www.osti.gov/servlets/purl/1471492.
@article{osti_1471492,
title = {Heteroleptic Nickel Complexes of a Bulky Bis(carbene)borate Ligand},
author = {Martinez, Jorge L. and Lee, Wei-Tsung and Pink, Maren and Chen, Chun-Hsing and Smith, Jeremy M.},
abstractNote = {Bis(carbene)borate ligand transfer to the nickel nitrosyl synthon Ni(NO)(PPh3)2Br provides the new nickel nitrosyl complex Ph2B(tBuIm)2Ni(NO)(PPh3). The solid state structure reveals a trigonal pyramidal nickel ion with a very long bond to the apical PPh3 ligand. The complex reversibly dissociates PPh3 in solution to afford three-coordinate Ph2B(tBuIm)2Ni(NO), with NMR data providing evidence for PPh3 binding at low temperatures. Ligand transfer to Ni(PMe3)2Cl2 provides the square planar complex, Ph2B(tBuIm)2Ni(PMe3)Cl, which shows no evidence for rearranging to the form a homoleptic complex with two bis(carbene)borate ligands. This complex is a suitable synthon for the [Ph2B(tBuIm)2Ni]+ fragment, as demonstrated by the synthesis of the π-allyl complex Ph2B(tBuIm)2Ni(η3-C7H7). The π-allyl complex reacts with O2 to provide benzaldehyde and an unstable complex that is tentatively identified as the nickel(II) hydroxide [Ph2B(tBuIm)2Ni(μ-OH)]2.},
doi = {10.1016/j.poly.2018.09.026},
journal = {Polyhedron},
number = 1,
volume = 156,
place = {United States},
year = {2018},
month = {9}
}

Journal Article:

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Bis(carbene)borate ligands to stabilize homoleptic and heteroleptic iron(II) complexes.

Save / Share:

Works referenced in this record:

Kinetics, Thermodynamics, and Effect of BPh 3 on Competitive C−C and C−H Bond Activation Reactions in the Interconversion of Allyl Cyanide by [Ni(dippe)]
journal, March 2004

  • Brunkan, Nicole M.; Brestensky, Donna M.; Jones, William D.
  • Journal of the American Chemical Society, Vol. 126, Issue 11
  • DOI: 10.1021/ja037002e

Cleavage of Carbon−Carbon Bonds in Alkyl Cyanides Using Nickel(0)
journal, August 2004

  • García, Juventino J.; Arévalo, Alma; Brunkan, Nicole M.
  • Organometallics, Vol. 23, Issue 16
  • DOI: 10.1021/om049700t

Solvent Effects and Activation Parameters in the Competitive Cleavage of C−CN and C−H Bonds in 2-Methyl-3-Butenenitrile Using [(dippe)NiH] 2
journal, July 2008

  • Swartz, Brett D.; Reinartz, Nicole M.; Brennessel, William W.
  • Journal of the American Chemical Society, Vol. 130, Issue 26
  • DOI: 10.1021/ja8000216

Evidence for the Existence of a Late-Metal Terminal Sulfido Complex
journal, April 1999

  • Vicic, David A.; Jones, William D.
  • Journal of the American Chemical Society, Vol. 121, Issue 16
  • DOI: 10.1021/ja984136x

Cationic Nickel(II) Complexes of Chelating N-Heterocyclic Carbenes
journal, October 1999

  • Douthwaite, Richard E.; Haüssinger, Daniel; Green, Malcolm L. H.
  • Organometallics, Vol. 18, Issue 22
  • DOI: 10.1021/om990398b

Nickel(II) cis - and trans -Dimethyl Complexes of Di-N-heterocyclic Carbenes
journal, June 2001

  • Douthwaite, Richard E.; Green, Malcolm L. H.; Silcock, Peter J.
  • Organometallics, Vol. 20, Issue 12
  • DOI: 10.1021/om010139y

Synthesis, structure and reactivity of NHC–nickel complexes containing carbonato ligands
journal, May 2013


Bis-NHC Chelate Complexes of Nickel(0) and Platinum(0)
journal, May 2014

  • Brendel, Matthias; Braun, Carolin; Rominger, Frank
  • Angewandte Chemie International Edition, Vol. 53, Issue 33
  • DOI: 10.1002/anie.201401024

Heteroleptic nickel( ii )–diNHC complexes and an unusual ‘reverse’ carbene-transfer reaction to silver( i )
journal, January 2017

  • Huynh, Han Vinh; Koh, Christine Hui Min; Nguyen, Van Ha
  • Dalton Transactions, Vol. 46, Issue 34
  • DOI: 10.1039/C7DT01912B

Organonickel complexes encumbering bis-imidazolylidene carbene ligands: Synthesis, X-ray structure and catalytic insights on Buchwald-Hartwig amination reactions
journal, March 2017


Four-coordinate Co( ii ) and Fe( ii ) complexes with bis(N-heterocyclic carbene)borate and their magnetic properties
journal, January 2015

  • Liu, Yuan-Zhong; Wang, Jing; Zhao, Yue
  • Dalton Transactions, Vol. 44, Issue 3
  • DOI: 10.1039/C4DT02537G

New Structural Motifs of Lithium N-Heterocyclic Carbene Complexes with Bis(3- tert -butylimidazol-2-ylidene)dialkylborate Ligands
journal, May 2009

  • Shishkov, Igor V.; Rominger, Frank; Hofmann, Peter
  • Organometallics, Vol. 28, Issue 12
  • DOI: 10.1021/om801097f

Synthesis and Unexpected Reactivity of Germyliumylidene Hydride [:GeH] + Stabilized by a Bis( N -heterocyclic carbene)borate Ligand
journal, July 2014

  • Xiong, Yun; Szilvási, Tibor; Yao, Shenglai
  • Journal of the American Chemical Society, Vol. 136, Issue 32
  • DOI: 10.1021/ja506824s

Metal Nitrosyls. I. Triphenylphosphine Nitrosyl Nickel Complexes
journal, January 1964


Four- and Five-Coordinate Nickel(II) Complexes with Trimethylphosphine.
journal, January 1969


Synthesis and structural characterization of [BseMe]Ni(PPh3)(NO), a nickel complex with a bent nitrosyl ligand
journal, October 2007


General bonding model for linear and bent transition metal-nitrosyl complexes
journal, May 1973


Neutral pyrazolyl-bridged nickel nitrosyl complexes. Synthesis, structure, and reactivity
journal, December 1979

  • Chong, Kenneth S.; Rettig, Steven J.; Storr, Alan
  • Canadian Journal of Chemistry, Vol. 57, Issue 23
  • DOI: 10.1139/v79-505

Insertion of Zerovalent Nickel into the N–N Bond of N-Heterocyclic-Carbene-Activated N 2 O
journal, August 2013

  • Tskhovrebov, Alexander G.; Solari, Euro; Scopelliti, Rosario
  • Inorganic Chemistry, Vol. 52, Issue 20
  • DOI: 10.1021/ic401524w

Reactivity of a Nickel Sulfide with Carbon Monoxide and Nitric Oxide
journal, September 2016

  • Hartmann, Nathaniel J.; Wu, Guang; Hayton, Trevor W.
  • Journal of the American Chemical Society, Vol. 138, Issue 38
  • DOI: 10.1021/jacs.6b08084

Direct Observation of Noninnocent Reactivity of ZnBr 2 with Alkyl Halide Complexes of Nickel
journal, January 2004

  • Anderson, Thomas J.; Vicic, David A.
  • Organometallics, Vol. 23, Issue 4
  • DOI: 10.1021/om034380j

Ring Closure of 1,4-Pentadiene to Cyclopentene by a Zwitterionic Nickel Catalyst
journal, August 2004

  • Wasilke, Julia-Christina; Komon, Zachary J. A.; Bu, Xianhui
  • Organometallics, Vol. 23, Issue 18
  • DOI: 10.1021/om049600n

Synthesis, characterization, and norbornene polymerization of η3-benzylnickel(II) complexes of N-heterocyclic carbenes
journal, June 2008


Unusual Reactivity of Molecular Oxygen with π-Allylnickel(N-heterocyclic carbene) Chloride Complexes
journal, January 2003

  • Dible, Benjamin R.; Sigman, Matthew S.
  • Journal of the American Chemical Society, Vol. 125, Issue 4
  • DOI: 10.1021/ja0286876

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.