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Inorganics 2017, 5(4), 84; https://doi.org/10.3390/inorganics5040084

Construction of a Planar Tetrapalladium Cluster by the Reaction of Palladium(0) Bis(isocyanide) with Cyclic Tetrasilane

1
Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba Meguro-ku, Tokyo 153-8580, Japan
2
Department of Applied Chemistry, School of Engineering, The University of Tokyo, 4-6-1 Komaba Meguro-ku, Tokyo 153-8580, Japan
3
Division of Molecular Science, Graduate School of Science and Technology, Gunma University, Kiryu, Gunma 376-8515, Japan
4
Institute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasugakoen Kasuga, Fukuoka 816-8580, Japan
*
Author to whom correspondence should be addressed.
Received: 6 November 2017 / Revised: 18 November 2017 / Accepted: 22 November 2017 / Published: 27 November 2017
(This article belongs to the Special Issue Coordination Chemistry of Silicon)
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Abstract

The planar tetrapalladium cluster Pd4{Si(iPr)2}3(CNtBu)4 (4) was synthesised in 86% isolated yield by the reaction of palladium(0) bis(isocyanide) Pd(CNtBu)2 with octaisopropylcyclotetrasilane (3). In the course of this reaction, the palladium atoms are clustered via insertion into the Si–Si bonds of 3, followed by extrusion of one SiiPr2 moiety and reorganisation to afford 4 with a 54-electron configuration. The CNtBu ligand in 4 was found to be easily replaced by N-heterocyclic carbene (iPr2IMMe) to afford the more coordinatively unsaturated cluster Pd4{Si(iPr)2}3(iPr2IMMe)3 (5) having the planar Pd4Si3 core. On the other hand, the replacement of CNtBu with a sterically compact ligand trimethylolpropane phosphite {P(OCH2)3CEt} led to a planar tripalladium cluster Pd3{Si(iPr)2}3{P(OCH2)3CEt}3 (6) and Pd{P(OCH2)3CEt}4 in 1:1 molar ratio as products. View Full-Text
Keywords: palladium; cluster; cyclic organopolysilane; template; bridging silylene ligand; isocyanide palladium; cluster; cyclic organopolysilane; template; bridging silylene ligand; isocyanide
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Sunada, Y.; Taniyama, N.; Shimamoto, K.; Kyushin, S.; Nagashima, H. Construction of a Planar Tetrapalladium Cluster by the Reaction of Palladium(0) Bis(isocyanide) with Cyclic Tetrasilane. Inorganics 2017, 5, 84.

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