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

Journal Article · · Polyhedron
 [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; Indiana University
  2. Indiana Univ., Bloomington, IN (United States). Dept. of Chemistry

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.

Research Organization:
New Mexico State Univ., Las Cruces, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Grant/Contract Number:
FG02-08ER15996
OSTI ID:
1471492
Alternate ID(s):
OSTI ID: 1636409
Journal Information:
Polyhedron, Journal Name: Polyhedron Journal Issue: 1 Vol. 156; ISSN 0277-5387
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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