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Unprecedented Formation of the First Alkaline‐Earth‐Metal Complex Bearing an Asymmetrical gem‐ Dithiolato Heteroscorpionato Ligand
Author(s) -
SánchezBarba Luis F.,
Garcés Andrés,
FernándezBaeza Juan,
Otero Antonio,
Honrado Manuel,
LaraSánchez Agustín,
Rodríguez Ana M.,
LópezSolera Isabel
Publication year - 2014
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.201301544
Subject(s) - chemistry , ligand (biochemistry) , alkaline earth metal , moiety , trigonal bipyramidal molecular geometry , metal , octahedron , crystallography , crystal structure , stereochemistry , reagent , manganese , magnesium , medicinal chemistry , organic chemistry , biochemistry , receptor
The reaction of the lithium dithioacetate derivative [Li(bdmpzdta)(THF)] [bdmpzdta = bis(3,5‐dimethylpyrazol‐1‐yl)dithioacetate] with 1 equiv. of C 3 H 5 MgCl proceeds in high yield to give the first alkaline‐earth‐metal complex bearing an asymmetrical gem ‐dithiolato moiety, namely, [Mg(κ 3 ‐NNS‐μ‐S‐bppbte)] 3 ( 1 ) [bppbte = 1,1‐bis(3,5‐dimethyl‐1 H ‐pyrazol‐1‐yl)pent‐4‐ene‐2,2‐bis(thiolate)]. This is achieved through an unprecedented insertion reaction of the allyl group into the C=S bond. In contrast, the reaction with the Grignard reagents MeMgCl or EtMgCl leads to the formation of the six‐coordinate sandwich species [Mg(κ 3 ‐bdmpzdta) 2 ] ( 2 ), as a result of a rapid ligand redistribution. The molecular structures of 1 and 2 in the solid state have been unambiguously established by single‐crystal X‐ray diffraction studies, which reveal a trinuclear entity with a twisted six‐membered core for 1 , in which all magnesium centers are arranged in a distorted trigonal bipyramidal geometry, whereas in 2 the magnesium center has an octahedral coordination environment with two heteroscorpionato ligands, which bind in a κ 3 ‐NNS fashion with a relative trans disposition.