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Activation of Heteroallenes CO x S 2– x ( x = 0–2): Experimental and Theoretical Evidence of the Synthetic Versatility of a Bulky Guanidinato Sm II Complex
Author(s) -
Castro Ludovic,
Mills David P.,
Jones Cameron,
Maron Laurent
Publication year - 2016
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.201501346
Subject(s) - chemistry , bimetallic strip , yield (engineering) , crystallography , valence (chemistry) , oxalate , reagent , computational chemistry , inorganic chemistry , metal , thermodynamics , organic chemistry , physics
A joint experimental/theoretical (DFT) study of the activation of heteroallenes CO x S 2– x ( x = 0–2) by [Sm(Giso) 2 ] {Giso – = [(ArN) 2 CNCy 2 ] – , Cy = cyclohexyl, Ar = 2,6‐diisopropylphenyl} is reported. All heteroallenes are reduced in a different manner. Indeed, while activation of CS 2 yields a bimetallic CS 2 coupled product through C–S bond formation, CO 2 forms an oxalate complex through C–C bond formation. This subsequently undergoes CO 2 insertion into one of its Sm–N bonds. Finally, COS activation is predicted to yield a dithiocarbonate complex, through the formation of an intermediate sulfido complex [(Giso) 2 Sm(µ‐S)Sm(Giso) 2 ]. Therefore, [Sm(Giso) 2 ] is a very versatile reagent, since it is a rare example of a complex that allows formation of several activation products involving valence isoelectronic substrates. This is rationalized by DFT calculations, and the latter emphasizes both the lack of kinetic stability of CS vs. CO and the high thermodynamic stability of the oxalate.