A new route to fluorocarbon-stabilized organoamidoplatinum(II) compounds—synthesis of a new isomer of [Me2)X(L)] (R = p-HC6F4 OR C6F5; X = Cl or I; L = unidentate ligand) complexes

Buxton, David P.; Deacon, Glen B.; James, Alison M.; Knowles, S. J.; Williams, Tracey

doi:10.1016/s0277-5387(00)86296-8

Cited by 5 publications

(2 citation statements)

References 14 publications

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“…or Tianjiao (Baotou, China) as ingots, powders or rods and stored under nitrogen in a glove box. Hg(C 6 F 5 ) 2 , 44 Hg(CCPh) 2 , 45 p-HC 6 F 4 NHC 2 H 4 NMe 2 (L Me H) 18,35 and p-HC 6 F 4 NHC 2 H 4 NEt 2 (L Et H) 18 were prepared by literature methods.…”

Section: Methodsmentioning

confidence: 99%

“…Although the ligands were initially prepared in a template synthesis on platinum to give potential 'rulebreaker' anticancer drugs, 33,34 the amine ligand precursors p-C 6 F 4 N(H)(CH 2 ) 2 NR 2 (R = Me, Et) are readily prepared by nucleophilic substitution between the amines R 2 N(CH 2 ) 2 NH 2 (R = Me, Et) and pentafluorobenzene. 18,35 So far, homoleptic rare earth complexes of L Me/Et ligands have not been isolated but formation of [Ln(L Me/Et ) 3 ] is favoured by charge balance for the Ln III state. Because such complexes would have crowded coordination spheres, there is uncertainty over the coordination number and whether N,N′,F-ligation and -CF-Ln bonding would be possible for some or all ligands.…”

Section: Introductionmentioning

confidence: 99%

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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

et al. 2012

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A new class of homoleptic organoamido rare earth complexes [Ln(L(Me) or L(Et))(3)] (Ln = La, Ce, Nd; L(Me/Et) = p-HC(6)F(4)N(CH(2))(2)NMe(2)/Et(2)) exhibiting (Ar)CF-Ln interactions has been isolated from redox-transmetallation/protolysis (RTP) reactions between the free metals, Hg(C(6)F(5))(2) and L(Me/Et)H in tetrahydrofuran, together with low yields of [Ln(L(Me))(2)F](3) (Ln = La, Ce) or [Nd(L(Et))(2)F](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; L(Et)) or a bidentate (N,N') ligand (Ln = Nd; L(Me)), in an unusual case of linkage variation. All (Ar)CF-Ln bond lengths are shorter than or similar to the corresponding Ln-NMe(2)/Et(2) bond lengths. In [Ln(L(Me))(2)F](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) L(Me) ligands, whilst [Nd(L(Et))(2)F](2) is a fluoride-bridged dimer.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2012

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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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Syntheses of reactive rare earth complexes by redox transmetallation/protolysis reactions–A simple and convenient method

Guo

Huo

Tan

et al. 2020

Coordination Chemistry Reviews

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A new route to fluorocarbon-stabilized organoamidoplatinum(II) compounds—synthesis of a new isomer of [Me2)X(L)] (R = p-HC6F4 OR C6F5; X = Cl or I; L = unidentate ligand) complexes

Cited by 5 publications

References 14 publications

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

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

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

Syntheses of reactive rare earth complexes by redox transmetallation/protolysis reactions–A simple and convenient method

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