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The Butterfly Complex [{Cp*Cr(CO)3 }2 (?,?1:1 -P4 )] as a Versatile Ligand and Its Unexpected P1 /P3 Fragmentation.

ABSTRACT: The versatile coordination behavior of the P4 butterfly complex [{Cp*Cr(CO)3 }2 (?,?1:1 -P4 )] (1) towards Lewis acidic pentacarbonyl compounds of Cr, Mo and W is reported. The reaction of 1 with [W(CO)4 (nbd)] (nbd=norbornadiene) yields the complex [{Cp*Cr(CO)3 }2 (?3 ,?1:1:1:1 -P4 ){W(CO)4 }] (2) in which 1 serves as a chelating P4 butterfly ligand. In contrast, reactions of 1 with [M(CO)4 (nbd)] (M=Cr (a), Mo (b)) result in the step-wise formation of [{Cp*Cr(CO)2 }2 (?3 ,?3:1:1 -P4 ){M(CO)5 }] (3?a,b) and [{Cp*Cr(CO)2 }2 -(?4 ,?3:1:1:1 -P4 ){M(CO)5 }2 ] (4?a,b) which contain a folded cyclo-P4 unit. Complex 4?a undergoes an unprecedented P1 /P3 -fragmentation yielding the cyclo-P3 complex [Cp*Cr(CO)2 (?3 -P3 )] (5) and the as yet unknown phosphinidene complex [Cp*Cr(CO)2 {Cr(CO)5 }2 (?3 -P)] (6). The identity of 6 is confirmed by spectroscopic methods and by the in situ formation of [{Cp*Cr(CO)2 (tBuNC)}P{Cr(CO)5 }2 (tBuNC)] (7). DFT calculations throw light on the bonding situation of the reported products.

SUBMITTER: Grunbauer R

PROVIDER: S-EPMC7540658 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature

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The Butterfly Complex [{Cp*Cr(CO)3 }2 (μ,η1:1 -P4 )] as a Versatile Ligand and Its Unexpected P1 /P3 Fragmentation.

Grünbauer Rebecca R Balázs Gábor G Scheer Manfred M

Chemistry (Weinheim an der Bergstrasse, Germany) 20200817 51

The versatile coordination behavior of the P4 butterfly complex [{Cp*Cr(CO)3 }2 (μ,η1:1 -P4 )] (1) towards Lewis acidic pentacarbonyl compounds of Cr, Mo and W is reported. The reaction of 1 with [W(CO)4 (nbd)] (nbd=norbornadiene) yields the complex [{Cp*Cr(CO)3 }2 (μ3 ,η1:1:1:1 -P4 ){W(CO)4 }] (2) in which 1 serves as a chelating P4 butterfly ligand. In ...[more]

PMID: 32657480

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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

The Butterfly Complex [{Cp*Cr(CO)3 }2 (?,?1:1 -P4 )] as a Versatile Ligand and Its Unexpected P1 /P3 Fragmentation.

Publications

The Butterfly Complex [{Cp*Cr(CO)<sub>3</sub> }<sub>2</sub> (μ,η<sup>1:1</sup> -P<sub>4</sub> )] as a Versatile Ligand and Its Unexpected P<sub>1</sub> /P<sub>3</sub> Fragmentation.

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