TY - JOUR
T1 - Construction of a planar tetrapalladium cluster by the reaction of palladium(0) bis(isocyanide) with cyclic tetrasilane
AU - Sunada, Yusuke
AU - Taniyama, Nobuhiro
AU - Shimamoto, Kento
AU - Kyushin, Soichiro
AU - Nagashima, Hideo
N1 - Funding Information:
This work was supported by the Core Research Evolutional Science and Technology (CREST) Program of Japan Science and Technology Agency (JST) Japan, the Cooperative Research Program of "Network Joint Research Center for Materials and Devices.", Grant in Aid for Scientific Research (B) (No. 16H04120) and Challenging Exploratory Research (No. 26620047) from the Ministry of Education, Culture, Sports, Science and Technology, Japan, the Iwatani Naoji Foundation, and the JFE 21st Century Foundation. This work was also supported by the special fund of Institute of Industrial Science, The University of Tokyo. The synchrotron radiation experiments were performed at the BL02B1 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal No. 2016A1118, 2016B1392, and 2017A1400)
Publisher Copyright:
© 2017 by the authors.
PY - 2017/12/1
Y1 - 2017/12/1
N2 - 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.
AB - 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.
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U2 - 10.3390/inorganics5040084
DO - 10.3390/inorganics5040084
M3 - Article
AN - SCOPUS:85045412198
SN - 2304-6740
VL - 5
JO - Inorganics
JF - Inorganics
IS - 4
M1 - 84
ER -