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Metalate-Mediated Functionalization of P₄ by Trapping Anionic [Cp*Fe(CO)₂(?¹-P₄)]^- with Lewis Acids.

ABSTRACT: The development of selective functionalization strategies of white phosphorus (P₄) is important to avoid the current chlorinated intermediates. The use of transition metals (TMs) could lead to catalytic procedures, but these are severely hampered by the high reactivity and unpredictable nature of the tetrahedron. Herein, we report selective first steps by reacting P₄ with a metal anion [Cp*Fe(CO)₂]^- (Cp*=C₅(CH₃)₅), which, in the presence of bulky Lewis acids (LA; B(C₆F₅)₃ or BPh₃), leads to unique TM-substituted LA-stabilized bicyclo[1.1.0]tetraphosphabutanide anions [Cp*Fe(CO)₂(?¹-P₄?LA)]^-. Their P-nucleophilic site can be subsequently protonated to afford the transient LA-free neutral butterflies exo,endo- and exo,exo-Cp*Fe- (CO)₂(?¹-P₄H), allowing controllable stepwise metalate-mediated functionalization of P₄.

SUBMITTER: Borger JE

PROVIDER: S-EPMC5474660 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature

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Publications

Metalate-Mediated Functionalization of P4 by Trapping Anionic [Cp*Fe(CO)2(η1-P4)]- with Lewis Acids.

Borger Jaap E JE Jongkind Maarten K MK Ehlers Andreas W AW Lutz Martin M Slootweg J Chris JC Lammertsma Koop K

ChemistryOpen 20170323 3

The development of selective functionalization strategies of white phosphorus (P4) is important to avoid the current chlorinated intermediates. The use of transition metals (TMs) could lead to catalytic procedures, but these are severely hampered by the high reactivity and unpredictable nature of the tetrahedron. Herein, we report selective first steps by reacting P4 with a metal anion [Cp*Fe(CO)2]- (Cp*=C5(CH3)5), whic ...[more]

PMID: 28638766

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Project description:Neutral {CpFeII(CO)2[SnII(Pc•3-)]} {Cp is cyclopentadienyl (1, 2) or Cp* is pentamethylcyclopentadienyl (3); Pc: phthalocyanine}, {Cp*FeII(CO)2[SnII(Nc•3-)]} (4, Nc: naphthalocyanine), and {CpFeII(CO)2[SnII(TPP•3-)]} (5, TPP: tetraphenylporphyrin) complexes in which CpFeII(CO)2 fragments (Cp: Cp or Cp*) are coordinated to SnII(macrocycle•3-) have been obtained. The product complexes were obtained at the reaction of charge transfer from CpFeI(CO)2 (Cp: Cp or Cp*) to [SnII(macrocycle2-)] to form the diamagnetic FeII and paramagnetic radical trianionic macrocycles. As a result, these formally neutral complexes contain S = 1/2 spins delocalized over the macrocycles. This provides alternation of the C-Nimine or C-Cmeso bonds in the macrocycles, the appearance of new bands in the near-infrared spectra of the complexes, and blue shift of both Soret and Q-bands. The {CpFeII(CO)2SnII(macrocycle•3-)} units (Cp: Cp or Cp*, macrocycle: Pc or Nc) form closely packed π-stacking dimers in 1 and 3 or one-dimensional chains in 2 and 4 with effective π-π interaction between the macrocycles. Such packing allows strong antiferromagnetic coupling between S = 1/2 spins. Magnetic interaction can be described well by the Heisenberg model for the isolated dimers in 1 and 3 with exchange interaction J/k B = -78 and -85 K, respectively. Magnetic behavior of 2 and 4 is described well by the model that includes contributions from an antiferromagnetically coupled S = 1/2 dimer (J intra) and a Heisenberg S = 1/2 chain with alternating antiferromagnetic spin exchange between the neighbors (J inter). Compound 2 demonstrates large intradimer interaction of J intra/k B = -54 K and essentially weaker interdimer exchange interactions of J inter/k B = -6 K, whereas compound 4 shows strong magnetic coupling of spins within the dimers (J intra/k B = -170 K) as well as between the dimers (J inter/k B = -40 K). Compound {CpFeII(CO)2[SnII(TPP•3-)]} (5) shows no π-π interactions between the porphyrin macrocycles, and magnetic coupling is weak in this case (Weiss temperature is -5 K). Preparation of a similar complex with indium(III) chloride phthalocyanine yields {CpFe(CO)2[In(Pc2-)]} (6). In this complex, indium(III) atoms are reduced instead of the phthalocyanine macrocycles that explains electron paramagnetic resonance silence of 6 in the 4-295 K range.

Dataset Information

Metalate-Mediated Functionalization of P₄ by Trapping Anionic [Cp*Fe(CO)₂(?¹-P₄)]^- with Lewis Acids.

Publications

Metalate-Mediated Functionalization of P<sub>4</sub> by Trapping Anionic [Cp*Fe(CO)<sub>2</sub>(η<sup>1</sup>-P<sub>4</sub>)]<sup>-</sup> with Lewis Acids.

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Dataset Information

Metalate-Mediated Functionalization of P4 by Trapping Anionic [Cp*Fe(CO)2(?1-P4)]- with Lewis Acids.

Publications

Metalate-Mediated Functionalization of P<sub>4</sub> by Trapping Anionic [Cp*Fe(CO)<sub>2</sub>(η<sup>1</sup>-P<sub>4</sub>)]<sup>-</sup> with Lewis Acids.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Metalate-Mediated Functionalization of P₄ by Trapping Anionic [Cp*Fe(CO)₂(?¹-P₄)]^- with Lewis Acids.