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Isolation of a New C s ‐Symmetrized Mo 3 (μ 3 ‐S)(μ‐S)(μ‐S 2 ) 2 Structural Type Through Complementary Association with a Cubane‐Type Mo 3 NiS 4 Cluster
Author(s) -
HernandezMolina Rita,
GonzalezPlatas Javier,
Vicent Cristian
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201101326
Subject(s) - chemistry , adduct , covalent bond , electrophile , nucleophile , crystallography , crystal structure , sulfide , stereochemistry , cluster (spacecraft) , cubane , medicinal chemistry , organic chemistry , catalysis , computer science , programming language
A new cluster of formula {[Mo 3 (μ 3 ‐S)(μ‐S)(μ‐S 2 ) 2 (dtp) 3 (μ‐OAc)][Mo 3 NiS 4 (dtp) 3 (μ‐OAc)(CH 3 CN)]} ( 1 ; dtp = diethyl dithiophosphate; OAc = acetate) comprising the novel C s ‐symmetrized Mo 3 (μ 3 ‐S)(μ‐S)(μ‐S 2 ) 2 structural type covalently attached to a cubane‐type Mo 3 NiS 4 core has been isolated and fully characterized. The reaction of a 2 M HCl solution of [Mo 3 S 4 (H 2 O) 9 ] 4+ with an excess of potassium diethyl dithiophosphate and acetic acid in the presence of the [Mo 3 (NiCl)S 4 (H 2 O) 9 ] 3+ cluster afforded a mixture of products encompassing different Mo 3 S x ( x = 4–7) cluster cores from which the Mo 3 (μ 3 ‐S)(μ‐S)(μ‐S 2 ) 2 structural type has been isolated in analytically pure form as a Mo 3 NiS 4 adduct. The robustness of the aggregate 1 was also retained in solution as judged by ESI‐MS and 31 P NMR techniques. Single‐crystal X‐ray analysis revealed in detail the complementary association of the newly formed Mo 3 (μ 3 ‐S)(μ‐S)(μ‐S 2 ) 2 entity and the Mo 3 NiS 4 cluster in which μ‐S sulfide ligands and μ‐S 2 disulfide ligands act as nucleophilic and electrophilic functional groups, respectively, towards the Mo 3 NiS 4 cube through directional Ni–S covalent bonds and short S···S contacts (below 3.3 Å).