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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]
+ Show Author Affiliations
  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. doi:10.1016/j.poly.2018.09.026.
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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
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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.
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@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 = {Tue Sep 25 00:00:00 EDT 2018},
month = {Tue Sep 25 00:00:00 EDT 2018}
}
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https://doi.org/10.1016/j.poly.2018.09.026
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Figures / Tables:

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