Highly electrophilic lanthanide complexes containing fluorinated amido ligands: multiple Ln···F interactions, agostic interactions and η6-arene coordination

Click, Damon R.; Scott, Brian L.; Watkin, John G.

doi:10.1039/a809275c

Cited by 53 publications

(54 citation statements)

References 19 publications

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“…[6] Related Eu II complexes with XC 6 F 5 (X = O, S) ligands have significantly longer bonds (e.g., […”

Section: Resultsmentioning

confidence: 99%

“…2.5 ). In most cases the polyfluoroaryl group is coordinated both through fluorine and another donor atom, for example, 1) carbon (C,F bridging [1] and C,F chelating [2][3][4][5] ) in polyfluorophenyl-rare-earth compounds, 2) nitrogen in polyfluorophenylamides, [6][7][8] 3) oxygen in polyfluorophenolates [9] and 4) sulfur in polyfluorothiolates. [10][11][12] In addition, BA C H T U N G T R E N N U N G (C 6 F 5 ) 4 À and related anions can act as C(Ar)-F-Ln donors, often chelating through two fluorine atoms.…”

Section: Introductionmentioning

confidence: 99%

“…Their existence is of considerable interest given the potential for rearrangement into the corresponding highly stable and insoluble LnF 3 compounds. In this paper, we report a series of ytterbium(II) polyfluoroorganoamides with strong C(Ar)-F-Yb coordination and that undergo C À F activation to give the fluoro(organoamido)lanthanoid cages [Yb 4 F 6 (L) 6 ] (L= p-HC 6 F 4 NA C H T U N G T R E N N U N G (CH 2 ) 2 NR 2 ; R= Et or Me). In each of the ytterbium complexes, as well as in the alkali metal derivatives prepared as metathesis reagents, the N,Ndialkyl-N'-2,3,5,6-tetrafluorophenyl-ethane-1,2-diamin-A C H T U N G T R E N N U N G ate(1À) ligands act as tridentate o-F,N,N' ligands and show strong C(Ar)-F-M binding.…”

Section: Introductionmentioning

confidence: 99%

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Intramolecular Metal–Fluorocarbon Coordination, CF Bond Activation and Lanthanoid–Fluoride Clusters with Tethered Polyfluorophenylamide Ligands

Deacon

Forsyth

Junk

et al. 2009

Chemistry A European J

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Activating C--F bonds: Strong metal-fluorocarbon coordination in complexes of electropositive metals (e.g., Na, K, Yb) with chelating polyfluorophenyl-substituted amide ligands is a precursor to C--F bond activation and fluoride abstraction when M=Yb(II), giving heteroleptic Yb(III) fluoride clusters (see scheme).Metalation of either N,N-diethyl- or N,N-dimethyl-N'-2,3,5,6-tetrafluorophenylethane-1,2-diamines (HL 1 a, 1 b respectively) with [M{N(SiMe(3))(2)}] (M=Na, K) or [Yb{N(SiMe(3))(2)}(2)(thf)(2)] yielded the metal-amido compounds [Na(L)] (2 a), [K(L)] (3 a) and [Yb(L)(2)(thf)(2)] (4 a, 4 b). The Yb complexes were also synthesised by redox transmetalation/ligand exchange from Yb, Hg(C(6)F(5))(2) and HL in THF or 4 a from a reaction of 3 a with YbI(2) in THF. In the presence of N,N,N',N'- tetramethyl-1,2-ethanediamine (TMEDA) the complexes 2 a and 3 a yielded [Na(L)(2)Na(tmeda)] (5 a) and [K(2)(L)(2)(tmeda)(2)] (6 a), respectively, as crystalline compounds, whilst crystallisation of 4 a from DME gave [Yb(L)(2)(dme)] (7 a). Their structures have chelating metal-amide and NR(2) donors and additional intramolecular M-F-C connectivity with relatively short bond lengths (Na--F 2.65-3.00 A; K--F 2.70-3.00 A; Yb--F 2.56 A). The Yb complexes undergo C--F activation in solution forming [Yb(4)(L)(6)F(6)] (8 a, 8 b). The connectivity of [Yb(4)(L)(6)F(6)], as shown by the X-ray structures, comprised a circular Yb(4)(mu-F)(4) periphery with two opposing Yb centres having either one L ligand and a Yb(2)(mu-F)(2) bridge or two L ligands. Each polyfluorophenylamide exhibits additional intramolecular Yb-F-C coordination from one of the ortho-F atoms resulting in seven or eight coordinate Yb centres. An attempt to synthesise 4 a by redox transmetalation/ligand exchange using Hg(C[triple chemical bond]CPh)(2) as the mercury reagent gave [Yb(4)(O)(2)(L)(4)(C[triple chemical bond]CPh)(4)(thf)(2)]THF (9 aTHF), most likely as a result of oxidation of the initially formed product.

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“…[6] Related Eu II complexes with XC 6 F 5 (X = O, S) ligands have significantly longer bonds (e.g., […”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Intramolecular Metal–Fluorocarbon Coordination, CF Bond Activation and Lanthanoid–Fluoride Clusters with Tethered Polyfluorophenylamide Ligands

Deacon

Forsyth

Junk

et al. 2009

Chemistry A European J

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“…The coordination sphere of monomeric tris Á/amido samarium complexes is usually completed with solvent molecules (as observed in [Sm(Nc -Hex 2 ) 3 (THF)] (D) [8a], {Sm[N(SiHMe 2 ) 2 ] 3 (THF) 2 } (E) [12] or [Sm(NHC 6 F 5 ) 3 (THF) 3 ] F [13]). Tetracoordinate ate complexes of tris-amido samarium(III) derivatives have also been structurally characterized, but only with an additional nitrogen-or oxygen-based anionic ligand [14].…”

Section: Resultsmentioning

confidence: 99%

Synthesis and structural characterization of unusual amido samarium(III) complexes

Martin‐Vaca

Dumitrescu

Bourissou

et al. 2003

Journal of Organometallic Chemistry

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“…In recent years DFDPA complexes s, p, d, and f elements gained some interest in the design of Lewis acids [4,[12][13][14][15], however the ligand stability and rearrangement was not the focus of these investigations.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular nucleophilic substitution in C6F5 moiety. The fluoride–dialkylamino exchange in decafluorodiphenlamino moiety

Shutov

Karlov

Harms

et al. 2009

Journal of Fluorine Chemistry

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Highly electrophilic lanthanide complexes containing fluorinated amido ligands: multiple Ln···F interactions, agostic interactions and η6-arene coordination

Cited by 53 publications

References 19 publications

Intramolecular Metal–Fluorocarbon Coordination, CF Bond Activation and Lanthanoid–Fluoride Clusters with Tethered Polyfluorophenylamide Ligands

Intramolecular Metal–Fluorocarbon Coordination, CF Bond Activation and Lanthanoid–Fluoride Clusters with Tethered Polyfluorophenylamide Ligands

Synthesis and structural characterization of unusual amido samarium(III) complexes

Intramolecular nucleophilic substitution in C6F5 moiety. The fluoride–dialkylamino exchange in decafluorodiphenlamino moiety

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