10.1002/anie.201800079
Angewandte Chemie International Edition
already at
a
catalyst/poison ratio of 5/1 (Scheme S1).[28]
conditions, the nanocluster displayed unprecedented catalytic
activity in hydrogenations of alkenes, alkynes and imines.
Extensions of such nanocluster preparation and applications to
small molecule activations are currently being explored.
Hydrogenation of α-cyclopropyl styrene was only slightly slower in
the presence of the homotopic poison dibenzo[a,e]cycloocta-
tetraene[29] (dct, 4 equiv. per Mn) which acted as a competing
substrate (see SI and entry 16, Table 2). These results are strong
indications of a heterotopic reaction mechanism which involves
polynuclear low-valent Mn species that form upon reductive Acknowledgement
activation of the nanocluster 2 with hydride reagents.
This work was funded by the European Research Council (ERC)
through a Consolidator grant (683150). S.D and F.M acknowledge
support from the University of Göttingen.
In summary, we have reported an unprecedented ladder-type
[XMnH]6 cluster that contains bulky amido ligands and active
hydrides. This nanosheet complements the small family of planar
3d transition metal clusters and presents a novel cluster topology.
The cluster is soluble in organic solvents; its crystals have been
studied by X-ray crystallography and solid state SQUID measure-
ments. The latter evidences strong antiferromagnetic exchange
interactions and a diamagnetic ground state of 2. Under reducing
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Keywords: manganese · hydrogenations · clusters · hydrides
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