Mono-, Di- and Tetranuclear Complexes and Clusters With Bromine-Functionalized Bis(diphenylphosphino)amine Ligands

Fliedel, Christophe; Pattacini, Roberto; Braunstein, Pierre

doi:10.1007/s10876-010-0315-9

Cited by 21 publications

(11 citation statements)

References 56 publications

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“…Characteristic 31 P{ 1 H} NMR resonances for ligands 1, 2, 1', and 2': 63.5 (1), 69.3 (2), 62.4 (1'), 67.9 (2') ppm (typical for N-alkyl or Naryl substituted DPPA type ligands). [4,5,16,17] The bis-chelated, dicationic Pd II complexes 3, 4, 3' and 4' were obtained by reaction of [Pd(NCMe) 4 ][BF 4 ] 2 (Scheme 2 b) with 2 equivalents of the respective ligand 1, 2, 1' and 2' (see the Supporting Information). Their upfield shifted 31 P{ 1 H} NMR singlets correspond to four equivalent coordinated P atoms: 48.4 (3), 55.5 (4), 46.7 (3'), 53.9 (4') ppm.…”

Section: Methodsmentioning

confidence: 99%

“…We therefore took advantage of readily accessible DPPA-type ligands (DPPA = Ph 2 PNHPPh 2 ), Nfunctionalized with a rigid para-thioether functionalized aryl group, [4] and of the stability of their chelate metal complexes. [5] Scheme 2 summarizes the synthetic route to complexes 3 and 4 (see the Experimental Section). The solid-state structure of 4 in 4·4 CH 2 Cl 2 (Figure 1) confirmed the bis-chelation of the Pd II centre and the desired position of the thioether groups, pointing in opposite directions from each other at the extremities of a rigid molecule (see the Supporting Information).…”

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Janus Microspheres for Visual Assessment of Molecular Interconnects

Fliedel

Faramarzi

Rosa

et al. 2013

Chemistry A European J

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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

Janus Microspheres for Visual Assessment of Molecular Interconnects

Fliedel

Faramarzi

Rosa

et al. 2013

Chemistry A European J

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“…Braunstein and colleagues reported the synthesis, via the classical aminolysis reaction, of two N -bromo-aryl-funtionalized DPPA-type ligands of the type Ph 2 PN(Ar)PPh 2 ( 226 , Ar = p -BrC 6 H 4 ; 227 , Ar = p -BrC 6 H 4 –C 6 H 4 ) and studied their coordination chemistry toward group 10 and 11 mononuclear metal precursors and Co(0) molecular clusters (Scheme ). Ligands 226 and 227 each exhibited a characteristic 31 P NMR singlet resonance at 70.8 and 69.8 ppm, respectively. As expected, their reaction with [MCl 2 (COD)] (M = Pd, Pt), in a 1:1 molar ratio, led to the formation of the corresponding neutral, square-planar complexes [MCl 2 ( 226 )] (M = Pd, 228 ; M = Pt, 230 ) and [PdCl 2 ( 227 )] ( 229 ) (Scheme ).…”

Section: Halogen Functionalizationsmentioning

confidence: 99%

Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands

2016

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The aim of this review is to highlight how the diversity generated by N-substitution in the well-known short-bite ligand bis(diphenylphosphino)amine (DPPA) allows a fine-tuning of the ligand properties and offers a considerable scope for tailoring the properties and applications of their corresponding metal complexes. The various N-substituents include nitrogen-, oxygen-, phosphorus-, sulfur-, halogen-, and silicon-based functionalities and directly N-bound metals. Multiple DPPA-type ligands linked through an organic spacer and N-functionalized DRPA-type ligands, in which the PPh2 substituents are replaced by PR2 (R = alkyl, benzyl) groups, are also discussed. Owing to the considerable diversity of N-functionalized DPPA-type ligands available, the applications of their mono- and polynuclear metal complexes are very diverse and range from homogeneous catalysis with well-defined or in situ generated (pre)catalysts to heterogeneous catalysis and materials science. In particular, sustained interest for DPPA-type ligands has been motivated, at least in part, by their ability to promote selective ethylene tri- or tetramerization in combination with chromium. Ligands and metal complexes where the N-substituent is a pure hydrocarbon group (as opposed to N-functionalization) are outside the scope of this review. However, when possible, a comparison between the catalytic performances of N-functionalized systems with those of their N-substituted analogs will be provided.

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“…Among the previously reported cobalt complexes, most Co 4 clusters are based on carbonyl ligands (Fliedel et al, 2010;De Silva et al, 2001;Darensbourg et al, 1986). However, oxime ligands usually coordinate to cobalt to form mononuclear complexes (Karabocek et al, 2012;Dutta & Gupta, 2011) and examples of multinuclear complexes are relatively scarce (Stamatatos et al, 2005(Stamatatos et al, , 2007.…”

Section: Figurementioning

confidence: 99%

A mixed-valence complex of cobalt based on 3-methoxysalicylaldoxime

Tiantian

Lü

et al. 2014

Acta Crystallogr C

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A new tetranuclear mixed-valence cobalt complex, namely di-μ2-azido-diazidodiethanolbis{μ2-2-[(hydroxyimino)methyl]-6-methoxyphenolato}bis{μ3-6-methoxy-2-[(oxidoimino)methyl]phenolato}dicobalt(II)dicobalt(III) ethanol disolvate, [Co(II)2Co(III)2(C8H7NO3)2(C8H8NO3)2(N3)4(C2H5OH)2]·2C2H5OH, has been synthesized by the reaction of Co(OAc)2·4H2O (OAc is acetate) with 3-methoxysalicylaldoxime (H2mosao) in an ethanol solution. In the complex, the four Co cations all display distorted octahedral coordination environments and they are bridged by two κ(2),κ(1),κ(1);μ3-mosao(2-) ligands, two κ(2),κ(2);μ2-Hmosao(-) ligands and two μ2-N3(-) anions to form a tetranuclear [Co4N4O4] cluster. Adjacent clusters are connected through weak C-H···N and C-H···O interactions, resulting in a two-dimensional supramolecular network parallel to the ac plane. The magnetic properties of the complex have also been studied.

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Mono-, Di- and Tetranuclear Complexes and Clusters With Bromine-Functionalized Bis(diphenylphosphino)amine Ligands

Cited by 21 publications

References 56 publications

Janus Microspheres for Visual Assessment of Molecular Interconnects

Janus Microspheres for Visual Assessment of Molecular Interconnects

Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands

A mixed-valence complex of cobalt based on 3-methoxysalicylaldoxime

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