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Title: Beta-Phosphinoethylboranes as Ambiphilic Ligands in Nickel-Methyl Complexes

Abstract

The ambiphilic {beta}-phosphinoethylboranes Ph{sub 2}PCH{sub 2}CH{sub 2}BR{sub 2} (BR{sub 2} = BCy{sub 2} (1a), BBN (1b)), which feature a ethano spacer CH{sub 2}CH{sub 2} between the Lewis acidic boryl and Lewis basic phosphino groups, were synthesized in nearly quantitative yields via the hydroboration of vinyldiphenylphosphine. Compounds 1a and 1b were fully characterized by elemental analysis, and by NMR and IR spectroscopy. X-ray crystallographic studies of compound 1b revealed infinite helical chains of the molecules connected through P{hor_ellipsis}B donor-acceptor interactions. The ability of these ambiphilic ligands to concurrently act as donors and acceptors was highlighted by their reactions with (dmpe)NiMe{sub 2}. Zwitterionic complexes (dmpe)NiMe(Ph{sub 2}PCH{sub 2}CH{sub 2}BCy{sub 2}Me) (2a) and (dmpe)NiMe(Ph{sub 2}PCH{sub 2}CH{sub 2}[BBN]Me) (2b) were generated via the abstraction of one of the methyl groups, forming a borate, and intramolecular coordination of the phosphine moiety to the resulting cationic metal center. Compound 2b was characterized by X-ray crystallography. Furthermore, B(C{sub 6}F{sub 5}){sub 3} abstracts the methyl group of a coordinated borate ligand to generate a free, 3-coordinate borane center in [(dmpe)NiMe(1a)]{sup +}[MeB(C{sub 6}F{sub 5}){sub 3}]{sup -} (3).

Authors:
; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
Chemical Sciences Division
OSTI Identifier:
1023396
Report Number(s):
LBNL-4663E
Journal ID: ISSN 0276-7333; ORGND7; TRN: US201118%%988
DOE Contract Number:  
DE-AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 27; Journal Issue: 6; Related Information: Journal Publication Date: March 2008; Journal ID: ISSN 0276-7333
Country of Publication:
United States
Language:
English
Subject:
37; BORANES; BORATES; CHAINS; CRYSTALLOGRAPHY; PHOSPHINES; SPACERS; SPECTROSCOPY

Citation Formats

Fischbach, Andreas, Bazinet, Patrick R, Waterman, Rory, and Tilley, T Don. Beta-Phosphinoethylboranes as Ambiphilic Ligands in Nickel-Methyl Complexes. United States: N. p., 2007. Web.
Fischbach, Andreas, Bazinet, Patrick R, Waterman, Rory, & Tilley, T Don. Beta-Phosphinoethylboranes as Ambiphilic Ligands in Nickel-Methyl Complexes. United States.
Fischbach, Andreas, Bazinet, Patrick R, Waterman, Rory, and Tilley, T Don. 2007. "Beta-Phosphinoethylboranes as Ambiphilic Ligands in Nickel-Methyl Complexes". United States. https://www.osti.gov/servlets/purl/1023396.
@article{osti_1023396,
title = {Beta-Phosphinoethylboranes as Ambiphilic Ligands in Nickel-Methyl Complexes},
author = {Fischbach, Andreas and Bazinet, Patrick R and Waterman, Rory and Tilley, T Don},
abstractNote = {The ambiphilic {beta}-phosphinoethylboranes Ph{sub 2}PCH{sub 2}CH{sub 2}BR{sub 2} (BR{sub 2} = BCy{sub 2} (1a), BBN (1b)), which feature a ethano spacer CH{sub 2}CH{sub 2} between the Lewis acidic boryl and Lewis basic phosphino groups, were synthesized in nearly quantitative yields via the hydroboration of vinyldiphenylphosphine. Compounds 1a and 1b were fully characterized by elemental analysis, and by NMR and IR spectroscopy. X-ray crystallographic studies of compound 1b revealed infinite helical chains of the molecules connected through P{hor_ellipsis}B donor-acceptor interactions. The ability of these ambiphilic ligands to concurrently act as donors and acceptors was highlighted by their reactions with (dmpe)NiMe{sub 2}. Zwitterionic complexes (dmpe)NiMe(Ph{sub 2}PCH{sub 2}CH{sub 2}BCy{sub 2}Me) (2a) and (dmpe)NiMe(Ph{sub 2}PCH{sub 2}CH{sub 2}[BBN]Me) (2b) were generated via the abstraction of one of the methyl groups, forming a borate, and intramolecular coordination of the phosphine moiety to the resulting cationic metal center. Compound 2b was characterized by X-ray crystallography. Furthermore, B(C{sub 6}F{sub 5}){sub 3} abstracts the methyl group of a coordinated borate ligand to generate a free, 3-coordinate borane center in [(dmpe)NiMe(1a)]{sup +}[MeB(C{sub 6}F{sub 5}){sub 3}]{sup -} (3).},
doi = {},
url = {https://www.osti.gov/biblio/1023396}, journal = {Organometallics},
issn = {0276-7333},
number = 6,
volume = 27,
place = {United States},
year = {Sun Oct 28 00:00:00 EDT 2007},
month = {Sun Oct 28 00:00:00 EDT 2007}
}