The effects of light lanthanoid elements (La, Ce, Nd) on (Ar)CF-Ln coordination and C-F activation in N,N-dialkyl-N '-2,3,5,6-tetrafluorophenylethane-1,2-diaminate complexes

Deacon, Glen B., Forsyth, Craig M., Junk, Peter C., Kelly, Rory P., Urbatsch, Aron, and Wang, Jun (2012) The effects of light lanthanoid elements (La, Ce, Nd) on (Ar)CF-Ln coordination and C-F activation in N,N-dialkyl-N '-2,3,5,6-tetrafluorophenylethane-1,2-diaminate complexes. Dalton Transactions, 41 (28). pp. 8624-8634.

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View at Publisher Website: http://dx.doi.org/10.1039/c2dt30604b
 
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Abstract

A new class of homoleptic organoamido rare earth complexes [Ln(LMe or LEt)3] (Ln = La, Ce, Nd; LMe/Et = p-HC6F4N(CH2)2NMe2/Et2) exhibiting (Ar)CF–Ln interactions has been isolated from redox–transmetallation/protolysis (RTP) reactions between the free metals, Hg(C6F5)2 and LMe/EtH in tetrahydrofuran, together with low yields of [Ln(LMe)2F]3 (Ln = La, Ce) or [Nd(LEt)2F]2 species, resulting from C–F activation reactions. The structures of the homoleptic complexes have eight-coordinate Ln metals with two tridentate (N,N′,F) amide ligands including (Ar)CF–Ln bonds and either a bidentate (N,F) ligand (Ln = La, Ce, Nd; LEt) or a bidentate (N,N′) ligand (Ln = Nd; LMe), in an unusual case of linkage variation. All (Ar)CF–Ln bond lengths are shorter than or similar to the corresponding Ln–NMe2/Et2 bond lengths. In [Ln(LMe)2F]3 (Ln = La, Ce) complexes, there is a six-membered ring framework with alternating F and Ln atoms and the metal atoms are eight-coordinate with two tridentate (N,N′,F) LMe ligands, whilst [Nd(LEt)2F]2 is a fluoride-bridged dimer.

Item ID: 29645
Item Type: Article (Research - C1)
ISSN: 1477-9234
Keywords: ray crystal-structures; bond activation; metal-complexes; organolanthanide fluoride; organometallic compounds; molecular-structure; catalytic-activity; amido ligands; divalent; exchange
Funders: Australian Research Council (ARC)
Projects and Grants: ARC DP0984775
Date Deposited: 02 Oct 2013 10:34
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030202 f-Block Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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