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Title: Intramolecular nucleophilic substitution on coordinated borabenzenes: A new entry into boratabenzene complexes

Abstract

Electrophilic complexes containing boratabenzene ligands are finding applications in olefin polymerization and oligomerization reactions. Most significant is the ability to control the reactivity of boratabenzene catalysts by adjusting the degree of orbital overlap between boron and its exocyclic substituent. Boratabenzene catalysts have appeared with reactivities that complement those observed with standard group 4 metallocenes. Furthermore, while both cyclopentadienyl (Cp) and boratabenzene are formally monoanionic 6{pi} electron donors, boratabenzene is a weaker donor. Isostructural complexes containing boratabenzene instead of Cp therefore have a greater tendency for lower oxidation states and offer altered mechanistic pathways for elementary reactions. One of the main difficulties in advancing a broader use of boratabenzene complexes in industry and in noncatalytic reactions useful for organic chemistry is the multistep synthesis of the boratabenzene complexes in industry and in noncatalytic reactions useful for organic chemistry is the multistep synthesis of the boratabenzene framework. Methods for coordination typically make direct analogy to Cp chemistry, namely, salt metathesis by addition of ligand salts to metal halides. In this paper the authors report a new type of reaction that gives transition metal-boratabenzene complexes directly from neutral borabenzene-base adducts.

Authors:
; ;
Publication Date:
Research Org.:
Univ. of California, Santa Barbara (US)
OSTI Identifier:
20000130
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 121; Journal Issue: 35; Other Information: PBD: 8 Sep 1999; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; CATALYSTS; ORGANIC BORON COMPOUNDS; CATALYTIC EFFECTS; LIGANDS; BENZENE; ADDUCTS

Citation Formats

Putzer, M., Rogers, J.S., and Bazan, G.C. Intramolecular nucleophilic substitution on coordinated borabenzenes: A new entry into boratabenzene complexes. United States: N. p., 1999. Web. doi:10.1021/ja9910661.
Putzer, M., Rogers, J.S., & Bazan, G.C. Intramolecular nucleophilic substitution on coordinated borabenzenes: A new entry into boratabenzene complexes. United States. doi:10.1021/ja9910661.
Putzer, M., Rogers, J.S., and Bazan, G.C. Wed . "Intramolecular nucleophilic substitution on coordinated borabenzenes: A new entry into boratabenzene complexes". United States. doi:10.1021/ja9910661.
@article{osti_20000130,
title = {Intramolecular nucleophilic substitution on coordinated borabenzenes: A new entry into boratabenzene complexes},
author = {Putzer, M. and Rogers, J.S. and Bazan, G.C.},
abstractNote = {Electrophilic complexes containing boratabenzene ligands are finding applications in olefin polymerization and oligomerization reactions. Most significant is the ability to control the reactivity of boratabenzene catalysts by adjusting the degree of orbital overlap between boron and its exocyclic substituent. Boratabenzene catalysts have appeared with reactivities that complement those observed with standard group 4 metallocenes. Furthermore, while both cyclopentadienyl (Cp) and boratabenzene are formally monoanionic 6{pi} electron donors, boratabenzene is a weaker donor. Isostructural complexes containing boratabenzene instead of Cp therefore have a greater tendency for lower oxidation states and offer altered mechanistic pathways for elementary reactions. One of the main difficulties in advancing a broader use of boratabenzene complexes in industry and in noncatalytic reactions useful for organic chemistry is the multistep synthesis of the boratabenzene complexes in industry and in noncatalytic reactions useful for organic chemistry is the multistep synthesis of the boratabenzene framework. Methods for coordination typically make direct analogy to Cp chemistry, namely, salt metathesis by addition of ligand salts to metal halides. In this paper the authors report a new type of reaction that gives transition metal-boratabenzene complexes directly from neutral borabenzene-base adducts.},
doi = {10.1021/ja9910661},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 35,
volume = 121,
place = {United States},
year = {1999},
month = {9}
}