Back to Table of Contents
46387-GB3
Enantioselective Dearomatization Agents Based on Chiral C2-Symmetric Ligands
Joseph M. Keane, Muhlenberg College
We are investigating a series of novel d6
molybdenum and tungsten complexes involving chiral C2-symmetric
tetraamine ligands. It is our hope that this work will lead to
the development of enantioselective dearomatization agents.
We note the recent development of pi-basic d6 molybdenum and
tungsten dearomatizing metal fragments by Harman et. al. as well as various
applications of chiral C2-symmteric tetraamine ligands in enantioselective syntheses.
To date, ligands of the type trans-N,N'-bis(heterocycle-2-methyl)cyclohexane-1,2-diamine have been
investigated primarily in the context of small, first-row transition metals,
and we suspect that heavy-metal complexes of such ligands
may have applications beyond those of the current project.
Prior to the current grant cycle, we established the
reaction of trans-N,N'-bis(heterocycle-2-methyl)cyclohexane-1,2-diamine ligands with molybdenum and tungsten hexacarbonyl
to give tridentate tricarbonyl complexes. For some variations of these tridentate
complexes, we were able to show that nitrosylation
followed by heating gives corresponding tetradentate mononitrosyl monocarbonyl
complexes. Depending on the specific
metal and ligand involved, some reactions gave a cis-beta ligand
topology, while others gave the desired cis-alpha
topology, in which the C2-symmetry of the ligand
is retained.
During the past year, we have determined that the above
reaction proceeds by substitution of a single linear nitrosyl
ligand for a carbonyl ligand
(Scheme 1). The corresponding tridentate mononitrosyl dicarbonyl complexes can be observed for molybdenum
variations and isolated for tungsten variations. For complexes involving pyridine-based
versions of the tetraamine ligand,
heating drives these tridentate mononitrosyl dicarbonyl complexes initially to the corresponding tetradentate cis-beta
mononitrosyl monocarbonyl
complexes and then to the corresponding tetradentate cis-alpha mononitrosyl
monocarbonyl complexes. The cause of the thermodynamic preference for
the cis-alpha form is not known, but
the complex identities are well-supported by 1H NMR and IR data as
well as several x-ray structures.
Two versions of the molybdenum tetradentate
cis-alpha mononitrosyl
monocarbonyl complexes have been oxidized using iodine
and bromine to give the corresponding d5 tetradentate
cis-alpha mononitrosyl
monohalide complexes, which we view as potential
direct precursors to dihapto aromatic complexes
(Scheme 2). Unfortunately, attempts to
bind aromatics by reducing these complexes in the presence of naphthalene and
other substrates have not been successful.
IR and electrochemical data suggest that the associated tetradentate mononitrosyl
pi-basic metal fragments are not quite as electron-rich as those which have previously
been demonstrated to form dihapto complexes with
aromatics. Data from our tridentate
complexes and tetradentate mononitrosyl
monocarbonyl complexes suggest that the corresponding
tungsten species are more electron-rich than their molybdenum congeners, and we
hope that this trend will hold true for the corresponding d5
tungsten halides.
ACS-PRF funds spent during the past year were used to
purchase our second MBraun Unilab
purge inert atmosphere glovebox. This box is used primarily for the above research
project and as such has allowed, in a very practical way, for greater involvement
of undergraduate research students in the project. Two students who participated in this project
during the 07-08 academic year had sufficient research
experience to successfully compete for NSF-REU fellowships during the summer of
2008. The box is also used by students
in our senior-level inorganic chemistry teaching lab, and in this way the
ACS-PRF support has benefited about a dozen students and will continue to
enhance the educational experience of many more in years to come.
We expect that a short paper detailing the synthesis and
characterization of several of the above complexes will be submitted for
publication shortly.
Back to top