Phospha-Fischer Carbenes: Synthesis, Structure, Bonding, and Reactions of Pd(0)− and Pt(0)−Phosphenium Complexes

Caputo, Christine A.; Jennings, Michael C.; Tuononen, Heikki M.; Jones, Nathan D.

doi:10.1021/om800973v

Cited by 51 publications

(59 citation statements)

References 102 publications

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“…26,27 Similar to previous work reported by our group, 44 we sought to employ a Lewis base to help support the coordinatively unsaturated phosphenium centre. In this regard, one equivalent of 2,2'-bipyridine (bpy) was added to 1PCl followed by the addition of Me3SiOTf (Scheme 5 The thermal stability of the cyclic four-membered diaminochlorophosphines was investigated given the multiple instances of a peak emerging at P ≈ 211 upon heating of these species.…”

Section: Otf = [F3cso3]¯)mentioning

confidence: 99%

Synthesis, Reactivity, and Computational Analysis of Halophosphines Supported by Dianionic Guanidinate Ligands

et al. 2012

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The reported chemistry and reactivity of guanidinate supported group 15 elements in the +3 oxidation state, particularly phosphorus, is limited when compared to their ubiquity in supporting metallic elements across the periodic table. We have synthesized a series of chlorophosphines utilizing homo-and heteroleptic (dianionic)guanidinates and have completed a comprehensive study of their reactivity. Most notable is the reluctancy of these four-membered rings to form the corresponding Nheterocyclic phosphenium cations, the tendency to chemically and thermally eliminate carbodiimide and the scarcely observed ring expansion by insertion of a chloro(imino)phosphine into a P-N bond of the P-N-C-N framework.Computational analysis has provided corroborating evidence for the unwillingness of the halide abstraction reaction by demonstrating the exceptional electron acceptor properties of the target phosphenium cations and the underscoring strength of the P-X bond.

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Section: Otf = [F3cso3]¯)mentioning

confidence: 99%

Synthesis, Reactivity, and Computational Analysis of Halophosphines Supported by Dianionic Guanidinate Ligands

et al. 2012

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“…The synthesis and purification of monophosphinated Fischer carbenes with various ligands and metals had been described in literature [25][26][27][28][29][30]. of molybdenum, chromium and tungsten but no crystal structures were determined [25].…”

Section: Synthesismentioning

confidence: 99%

Conformation analysis of triphenylphosphine in trans and cis triphenylphosphine-substituted Fischer carbene complexes

Landman

Levell

Rooyen

et al. 2014

Journal of Molecular Structure

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“…The cations are weak donors and strong acceptors, thus enabling NHPs to be good Lewis acidic ligands for electron-rich transition metals. [8][9][10] The NHP framework typically consists of four-, five-, or sixmembered rings with phosphorus being the lone reactive site. The main focus in this field has been to harness the chemistry of the P + centre; however, a shifting philosophy within main group chemistry as a whole (which includes phosphenium chemistry) has moved from studying purely the fundamental structure, bonding, and reactivity of these species to their potential for applications in broader arenas.…”

Section: Introductionmentioning

confidence: 99%

“…15), 3089(10) 1. H NMR (CDCl 3 ␦ (ppm)): 8.72 (s, 2H),8.04 (s, 2H, thienyl), 7.08 (m, 6H, phenyl), 2.94 (sept., 4H, 3 J HH = 6.8 Hz), 1.10 (d, 24H, 3 J HH = 6.8 Hz) 13.…”

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A phosphenium cation supported by a seven-membered thiophene based ring system

2013

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A novel diamine ligand containing a simple thiophene ring in the backbone has been synthesized. Substitution at the nitrogen atoms with either 2,4,6-trimethylphenyl (Mes) or 2,6-diisopropylphenyl (Dipp) was varied via a condensation reaction between the corresponding aniline and 3,4-diformylthiophene, giving two different ligand derivatives. In onwards chemistry that targeted the cyclic diaminochlorophosphines, the substitution at phosphorus was dependent on the ligand used. For example, when a stoichiometric reaction between PCl 3 and thiophene-3,4 diyldimethaneamine (R = Mes) was carried out, the synthesis of a bis-substituted diphosphino-product was isolated. If the R = Dipp ligand derivative was employed, both a 2:1 and 1:1 stoichiometric reaction between PCl 3 and the diamine was observed. Nevertheless, the cyclic diaminochlorophosphine (i.e., 1:1 stoichiometry) for R = Dipp was isolated in high yields and the synthesis of the corresponding phosphenium cation was achieved and structurally characterized.Résumé : On a synthétisé un nouveau ligand diamine dont le squelette contient un noyau thiophène simple. On a procédé à la substitution d'un groupe 2,4,6-triméthylphényle (Mes) ou d'un groupe 2,6-diisopropylphényle (Dipp) sur les atomes d'azote par une réaction de condensation entre l'aniline correspondante et le 3,4-diformylthiophène pour obtenir deux dérivés différents du ligand. Lors de réactions chimiques ultérieures ayant pour cible les diaminochlorophosphines cycliques, la substitution sur le phosphore dépendait du ligand utilisé. Par exemple, une réaction stoechiométrique entre PCl3 et la thiophène-3, 4 diyldiméthanamine (R = Mes) a donné la synthèse d'un produit diphosphiné bisubstitué. Lorsqu'on a employé le dérivé R = Dipp du ligand, on a observé une réaction de stoechiométrie 2:1 ainsi qu'une réaction de stoechiométrie 1:1 entre PCl3 et la diamine. Néanmoins, on a isolé avec un haut rendement la diaminochlorophosphine cyclique (c. à d. stoechiométrie 1:1) obtenue pour R = Dipp, et on a synthétisé le cation phosphénium correspondant et caractérisé sa structure. [Traduit par la Rédaction]

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Phospha-Fischer Carbenes: Synthesis, Structure, Bonding, and Reactions of Pd(0)− and Pt(0)−Phosphenium Complexes

Abstract: The analogy between cationic Group 10 metal-phosphenium complexes and Fischer carbenes has been formalized through structural and reactivity studies, and by energy decomposition analysis (EDA) of the M-P bond. The studied compounds were the three-

Cited by 51 publications

References 102 publications

Synthesis, Reactivity, and Computational Analysis of Halophosphines Supported by Dianionic Guanidinate Ligands

Synthesis, Reactivity, and Computational Analysis of Halophosphines Supported by Dianionic Guanidinate Ligands

Conformation analysis of triphenylphosphine in trans and cis triphenylphosphine-substituted Fischer carbene complexes

A phosphenium cation supported by a seven-membered thiophene based ring system

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