Issue 13, 2012
From the journal:

Dalton Transactions

Electronic structures of methylated azaferrocenes and their borane adducts: Photoelectron spectroscopy and electronic structure calculations†

Tim J. Brunker,*a   Branka Kovač,b   Konrad Kowalski,c   Walther Polit,d   Rainer F. Winter,d   Arnold L. Rheingolde  and  Igor Novak*f  

* Corresponding authors

a Department of Chemistry, Jess and Mildred Fisher College of Science and Mathematics, Towson University, 8000 York Road, Towson, MD 21252, USA
E-mail: tbrunker@towson.edu

b Ruđer Bošković Institute, Bijenička cesta 54, HR-10000 Zagreb, Croatia
E-mail: bkovac@irb.hr

c Department of Organic Chemistry, Faculty of Chemistry, University of Łódź, Tamka 12, 91-403 Łódź, Poland
E-mail: kondor15@wp.pl

d Fachbereich Chemie, Universität Konstanz, Universitätstraße 10, D-78453 Konstanz, Germany
E-mail: rainer.winter@uni-konstanz.de

e Department of Chemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093, USA
E-mail: arheingold@ucsd.edu

f Charles Sturt University, POB 883, Orange NSW 2800, Australia
E-mail: inovak@csu.edu.au

Abstract

The preparation and crystal structure of a new 2,5-dimethylazaferrocene (DMAF) adduct of borane (DMAF–BH3) are reported. The electronic structures of 1,2,3,4,5-pentamethylazaferrocene (PMAF), its borane adduct 1,2,3,4,5-pentamethylazaferrocene–BH3 (PMAF–BH3) and of DMAF–BH3 have been studied by HeI–HeII UV photoelectron spectroscopy (UPS) and high-level DFT methods. UPS data reveal the influence of borane and methyl substitution on the electronic structures of azaferrocenes, which have been rationalized by inductive and hyperconjugative effects. UPS data also allow for the estimation of azaferrocene lone-pair stabilization upon coordination to borane, and suggest that pyridine is a slightly stronger sigma donor toward BH3 than either azaferrocene studied. UV-Vis spectroscopic data for the radical cation of PMAF were also obtained and compared with the UPS data.

Graphical abstract: Electronic structures of methylated azaferrocenes and their borane adducts: Photoelectron spectroscopy and electronic structure calculations

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Article information

DOI
https://doi.org/10.1039/C2DT12237E
Article type
Paper
Submitted
22 Nov 2011
Accepted
05 Jan 2012
First published
14 Feb 2012

Dalton Trans., 2012,41, 3675-3683

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Electronic structures of methylated azaferrocenes and their borane adducts: Photoelectron spectroscopy and electronic structure calculations

T. J. Brunker, B. Kovač, K. Kowalski, W. Polit, R. F. Winter, A. L. Rheingold and I. Novak, Dalton Trans., 2012, 41, 3675 DOI: 10.1039/C2DT12237E

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