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• W2147698720 endingPage "14334" @default.
• W2147698720 startingPage "14322" @default.
• W2147698720 abstract "Abstract The preparation and comprehensive characterization of a series of homoleptic sandwich complexes containing diphosphacyclobutadiene ligands are reported. Compounds [K([18]crown‐6)(thf) 2 ][Fe(η 4 ‐P 2 C 2 t Bu 2 ) 2 ] (K 1 ), [K([18]crown‐6)(thf) 2 ][Co(η 4 ‐P 2 C 2 t Bu 2 ) 2 ] (K 2 ), and [K([18]crown‐6)(thf) 2 ][Co(η 4 ‐P 2 C 2 Ad 2 ) 2 ] (K 3 , Ad=adamantyl) were obtained from reactions of [K([18]crown‐6)(thf) 2 ][M(η 4 ‐C 14 H 10 ) 2 ] (M=Fe, Co) with t BuCP ( 1 , 2 ), or with AdCP ( 3 ). Neutral sandwiches [M(η 4 ‐P 2 C 2 t Bu 2 ) 2 ] ( 4 : M=Fe 5 : M=Co) were obtained by oxidizing 1 and 2 with [Cp 2 Fe]PF 6 . Cyclic voltammetry and spectro‐electrochemistry indicate that the two [M(η 4 ‐P 2 C 2 t Bu 2 ) 2 ] − /[M(η 4 ‐P 2 C 2 t Bu 2 ) 2 ] moieties can be reversibly interconverted by one electron oxidation and reduction, respectively. Complexes 1 – 5 were characterized by multinuclear NMR, EPR ( 1 and 5 ), UV/Vis, and Mössbauer spectroscopies ( 1 and 4 ), mass spectrometry ( 4 and 5 ), and microanalysis ( 1 – 3 ). The molecular structures of 1 – 5 were determined by using X‐ray crystallography. Essentially D 2 d ‐symmetric structures were found for all five complexes, which show the two 1,3‐diphosphacyclobutadiene rings in a staggered orientation. Density functional theory calculations revealed the importance of covalent metal–ligand π bonding in 1 – 5 . Possible oxidation state assignments for the metal ions are discussed." @default.
• W2147698720 created "2016-06-24" @default.
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• W2147698720 date "2010-12-01" @default.
• W2147698720 modified "2023-10-18" @default.
• W2147698720 title "Homoleptic Diphosphacyclobutadiene Complexes [M(η4-P2C2R2)2]x− (M=Fe, Co; x=0, 1)" @default.
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