ChemInform Abstract: Chemistry of ((Cr(cp)(CO)3)2), (cp: η5‐C5H5). Reaction with Elemental P4. A High Yield Synthesis and Crystal Structures of ((Cr(cp)(CO)2)2(.mu±eta.2‐P2)) and (Cr(cp)(CO)2(η3‐P3)).

Goh, Lai Yoong; Chu, Chit‐Kay; Wong, Richard C. S.; Hambley, T. W.

doi:10.1002/chin.199003241

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“…The pentaphosphacyclopentadienyl anion can also form triple-decker sandwich structures. An interesting such triple-decker sandwich compound is the chromium derivative Cp 2 Cr 2 (μ-η, 5 η 5 -P 5 ) synthesized from P 4 and Cp 2 Cr 2 (CO) 6 by Goh and co-workers − and subsequently studied by Scheer and co-workers . In connection with the synthesis of this triple-decker sandwich, several interesting intermediates are isolated from the Cp 2 Cr 2 (CO) 6 /P 4 system including the triphosphacyclopropenyl complex CpCr(CO) 2 (η 3 -P 3 ) and the diphosphaacetylene complex Cp 2 Cr 2 (CO) 4 (μ-η 2 -P 2 ) (Figure ).…”

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confidence: 99%

Mechanism for the Reaction of White Phosphorus with Cp₂Cr₂(CO)₆ Leading Ultimately to the Triple-Decker Sandwich Cp₂Cr₂(μ-η⁵,η⁵-P₅): A Theoretical Study

Zhong

Yang

et al. 2021

Inorg. Chem.

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The experimentally known reaction of Cp 2 Cr 2 (CO) 6 with white phosphorus (P 4 ) to give CpCr(CO) 2 (η 3 -P 3 ), Cp 2 Cr 2 (CO) 4 (μ-η, 2 η 2 -P 2 ), and the triple-decker sandwich Cp 2 Cr 2 (μ-η, 5 η 5 -P 5 ) is of interest since the P 4 reactant having a tetrahedral cluster of four phosphorus atoms is converted to products having P 2 , P 3 , and P 5 ligands. The mechanism of this obviously complicated reaction can be dissected into three stages using a coupled cluster theoretical method that has been benchmarked with the P 2 , Mn(CO) 5 , and CpCr(CO) 3 dimerization processes. The first stage of the Cp 2 Cr 2 (CO) 6 /P 4 reaction mechanism generates the unsaturated singlet intermediate Cp 2 Cr 2 (CO) 5 that combines with the P 4 reactant. Decarbonylation of the resulting Cp 2 Cr 2 (CO) 5 (P 4 ) complex provides a singlet tetracarbonyl readily fragmenting into the stable triphosphacyclopropenyl complex CpCr(CO) 2 (η 3 -P 3 ) and the chromium phosphide CpCr(CO) 2 (P). The isomeric triplet tetracarbonyl Cp 2 Cr 2 (CO) 4 (P 4 ), readily fragments into CpCr(CO) 2 (η 2 -P 2 ), which can generate the stable diphosphaacetylene complex Cp 2 Cr 2 (CO) 4 (η, 2 η 2 -P 2 ) as well as the pentamer [CpCr(CO) 2 ] 5 (P 10 ). Combination of the coordinately unsaturated CpCr(CO)(η 3 -P 3 ) with CpCr(CO) 2 (η 2 -P 2 ) can lead to a ring expansion. This generates the P 5 pentagonal ligand in a Cp 2 Cr 2 (CO) 3 (P 5 ) precursor to the experimentally observed carbonyl-free triple-decker sandwich Cp 2 Cr 2 (μ-η, 5 η 5 -P 5 ) after three successive decarbonylations.

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Section: Introductionmentioning

confidence: 99%

Mechanism for the Reaction of White Phosphorus with Cp₂Cr₂(CO)₆ Leading Ultimately to the Triple-Decker Sandwich Cp₂Cr₂(μ-η⁵,η⁵-P₅): A Theoretical Study

Zhong

Yang

et al. 2021

Inorg. Chem.

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ChemInform Abstract: Chemistry of ((Cr(cp)(CO)3)2), (cp: η5‐C5H5). Reaction with Elemental P4. A High Yield Synthesis and Crystal Structures of ((Cr(cp)(CO)2)2(.mu±eta.2‐P2)) and (Cr(cp)(CO)2(η3‐P3)).

Abstract: A radical mechanism is postulated for the formation of the two air‐stable title complexes (III) (space group P21/n, Z=4) and (IV) (P21/c, Z = 8).

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Mechanism for the Reaction of White Phosphorus with Cp₂Cr₂(CO)₆ Leading Ultimately to the Triple-Decker Sandwich Cp₂Cr₂(μ-η⁵,η⁵-P₅): A Theoretical Study

Mechanism for the Reaction of White Phosphorus with Cp₂Cr₂(CO)₆ Leading Ultimately to the Triple-Decker Sandwich Cp₂Cr₂(μ-η⁵,η⁵-P₅): A Theoretical Study

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ChemInform Abstract: Chemistry of ((Cr(cp)(CO)3)2), (cp: η5‐C5H5). Reaction with Elemental P4. A High Yield Synthesis and Crystal Structures of ((Cr(cp)(CO)2)2(.mu±eta.2‐P2)) and (Cr(cp)(CO)2(η3‐P3)).

Abstract: A radical mechanism is postulated for the formation of the two air‐stable title complexes (III) (space group P21/n, Z=4) and (IV) (P21/c, Z = 8).

Cited by 1 publication

References 1 publication

Mechanism for the Reaction of White Phosphorus with Cp2Cr2(CO)6 Leading Ultimately to the Triple-Decker Sandwich Cp2Cr2(μ-η5,η5-P5): A Theoretical Study

Mechanism for the Reaction of White Phosphorus with Cp2Cr2(CO)6 Leading Ultimately to the Triple-Decker Sandwich Cp2Cr2(μ-η5,η5-P5): A Theoretical Study

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Mechanism for the Reaction of White Phosphorus with Cp₂Cr₂(CO)₆ Leading Ultimately to the Triple-Decker Sandwich Cp₂Cr₂(μ-η⁵,η⁵-P₅): A Theoretical Study

Mechanism for the Reaction of White Phosphorus with Cp₂Cr₂(CO)₆ Leading Ultimately to the Triple-Decker Sandwich Cp₂Cr₂(μ-η⁵,η⁵-P₅): A Theoretical Study