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Distannabarrelenes with Three Coordinated Sn^II Atoms.

ABSTRACT: Crystalline 1,4-distannabarrelene compounds [(ADC^Ar )₃ Sn₂ ]SnCl₃ (3-Ar) (ADC^Ar ={ArC(NDipp)₂ CC}; Dipp=2,6-iPr₂ C₆ H₃ , Ar=Ph or DMP; DMP=4-Me₂ NC₆ H₄ ) derived from anionic dicarbenes Li(ADC^Ar ) (2-Ar) (Ar=Ph or DMP) have been reported. The cationic moiety of 3-Ar features a barrelene framework with three coordinated Sn^II atoms at the 1,4-positions, whereas the anionic unit SnCl₃ is formally derived from SnCl₂ and chloride ion. The all carbon substituted bis-stannylenes 3-Ar have been characterized by NMR spectroscopy and X-ray diffraction. DFT calculations reveal that the HOMO of 3-Ph (ϵ=-6.40 eV) is mainly the lone-pair orbital at the Sn^II atoms of the barrelene unit. 3-Ar readily react with sulfur and selenium to afford the mixed-valence Sn^II /Sn^IV compounds [(ADC^Ar )₃ SnSn(E)](SnCl₆ )_0.5 (E=S 4-Ar, Ar=Ph or DMP; E=Se 5-Ph).

SUBMITTER: Sharma MK

PROVIDER: S-EPMC7496072 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature

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Distannabarrelenes with Three Coordinated SnII Atoms.

Sharma Mahendra K MK Glodde Timo T Neumann Beate B Stammler Hans-Georg HG Ghadwal Rajendra S RS

Chemistry (Weinheim an der Bergstrasse, Germany) 20200728 49

Crystalline 1,4-distannabarrelene compounds [(ADCAr )3 Sn2 ]SnCl3 (3-Ar) (ADCAr ={ArC(NDipp)2 CC}; Dipp=2,6-iPr2 C6 H3 , Ar=Ph or DMP; DMP=4-Me2 NC6 H4 ) derived from anionic dicarbenes Li(ADCAr ) (2-Ar) (Ar=Ph or DMP) have been reported. The cationic moiety of 3-Ar features a barrelene framework with three coordinated SnII atoms at the 1,4-pos ...[more]

PMID: 32216071

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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

Distannabarrelenes with Three Coordinated Sn^II Atoms.

Publications

Distannabarrelenes with Three Coordinated Sn<sup>II</sup> Atoms.

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