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Updated: Jun 4, 2025

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
Published on: April 10, 2018
A sulfur-templated Ni-Ni' coordination polymer that relies on a polarizable nickel nitrosyl hub
Manish Jana1, Michael B Hall1, Marcetta Y Darensbourg1
1Department of Chemistry, Texas A & M University, College Station, Texas 77843, USA. hall@science.tamu.edu.
Abstract:
The templating properties of a diaza-nickel-cis-dithiolate towards triphenylphosphine gold(I), yielding a transoid [Ni(N2S2)·2Au(PPh3)] complex (T. A. Pinder, S. K. Montalvo, A. M. Lunsford, C.-H. Hsieh, J. H. Reibenspies and M. Y. Darensbourg, Dalton Trans., 2014, 43, 138-144) suggested that a suitable analogue of d10-Au(I), i.e., {Ni(NO)}10, could generate a tetrahedral nickel node for a [Ni(N2S2)·2Ni(NO)(X)] coordination polymer. Monomeric precursors, derived from Feltham's [(Ph3P)2Ni(NO)(Cl)] (R. D. Feltham, Inorg. Chem., 1964, 3, 116-119) produced the bidentate/sulfur-chelated [Ni(N2S2)·Ni(NO)(X)] species with loss of PPh3. Exchange of Cl- by azide, N3-, in the {Ni(NO)}10 synthon led to the balance of electrophilicity at Ni(NO) and non-covalent (H-bonding and van der Waals) interactions that stabilized the extended chain of bridging sulfurs, in transoid connectivities, between a square planar NiII and a tetrahedral Ni, the latter within the electronic and spin-delocalized {Ni(NO)}10 system. This study defines a new path that creates coordination polymers using metallodithiolates, the success of which, in this case, depends on the highly polarizable {Ni(NO)}10 unit.
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