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Reactions of exo ‐Substituted RSn 9 3− Clusters with Pd: Endohedral Cluster Formation and Oxidative Insertion
Author(s) -
Kocak F. Sanem,
Zavalij Peter,
Eichhorn Bryan
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201002019
Subject(s) - chemistry , crystallography , cluster (spacecraft) , stoichiometry , substituent , oxidative addition , ethylenediamine , atom (system on chip) , stereochemistry , pyridine , ion , transition metal , medicinal chemistry , inorganic chemistry , catalysis , organic chemistry , computer science , embedded system , programming language , biochemistry
Pyridine/ethylenediamine solutions of [Sn 9 SnCy 3 ] 3− ( 1 ) react with [Pd(PPh 3 ) 4 ] to give new clusters [Pd@Sn 9 SnCy 3 ] 3− ( 2 ) and [Pd@Sn 9 PdSnCy 3 ] 3− ( 3 ), depending on stoichiometry. These compounds are formed sequentially and are the first transition metal derivates of exo ‐substituted Zintl clusters. Oxidative insertion of a Pd atom into the Pd@Sn 9 SnCy 3 bond of 2 to form 3 represents a new reaction type for Zintl cluster compounds. The conversion Sn 9 4− → 1 → 2 → 3 is a rare case in which charge and mass are conserved in a series of Zintl clusters. Complexes 1 , 2 , and 3 are all highly fluxional in solution. In all three clusters, the nine Sn vertices are in rapid exchange on the NMR timescale. In 1 and 2 , the exo ‐SnCy 3 substituent also scrambles intramolecularly around the outside of the clusters. In 3 , the SnCy 3 group remains attached to the vertex Pd atom. The disparate reactions with the other RSn 9 3− ions are discussed.