Oxidative Coupling of the Selenolate Functions in (C6H5)3PC(Se)P(C6H5)3: Crystal Structure of {[(C6H5)3P]2CSe}Fe2OCl·4CH2Cl2 Containing a Linear FeOFe Axis

Schmidbaur, Hubert; Zybill, Christian; Neugebauer, Dietmar

doi:10.1002/anie.198301561

Cited by 14 publications

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“…Curiously, this process is the opposite of that found in the reaction of the carbodiphosphorane selenolate zwitterion PPh 3 C(Se)PPh 3 with iodine, which leads to the coupling of two selenolate functions upon oxidation to afford the cation [(PPh 3 ) 2 C-Se-Se-C(PPh 3 ) 2 ] 2þ . 27…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Se−Se Bond Breaking of Polyselenides Containing Pendant Diphosphine Complexes of Manganese(I)

Ruiz¹,

Arauz²,

Ceroni³

et al. 2010

Organometallics

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Reaction of [Mn(CO) 4 {(PPh 2 ) 2 CH}] (1) with half an equivalent of dipiperidinotetraselane affords the tetraselenide compoundwhich, upon treatment with KOH, is transformed into the corresponding triselenide and diselenide derivatives 2-Se 3 and 2-Se 2 . Full or partial protonation of the methanide carbon atoms can be accomplished by reaction of the above compounds with HBF 4 , whereas treatment of 2-Se 2 with I 2 gives rise to the formation of the selenelyl iodide derivative [Mn(CO) 4 {(PPh 2 ) 2 C-Se-I}] (5).

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Section: Resultsmentioning

confidence: 99%

Synthesis and Se−Se Bond Breaking of Polyselenides Containing Pendant Diphosphine Complexes of Manganese(I)

Ruiz¹,

Arauz²,

Ceroni³

et al. 2010

Organometallics

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“…The same reactivity toward selenium , and tellurium was explored by the same group (equations 1 and 2 in Scheme , respectively). More intriguing were the results achieved in presence of mild oxidants such as elemental bromine, elemental iodine, or FeCl 3 that formed the dication [ 586 ] 2+ through an oxidative coupling of two selenolate functions. , The X-ray structures of the selenide cation [ 585 ] + and dication [ 586 ] 2+ proved the planarity of the ylidic carbon in both compounds, the dication displaying an unusual Se–Se bond distance of 2.492(2) Å.…”

Section: Geminal Dianions Of Type III (A and B: Cationic Fragments)mentioning

confidence: 99%

Geminal Dianions Stabilized by Main Group Elements

2019

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This review is dedicated to the chemistry of stable and isolable species that bear two lone pairs at the same C center, i.e. geminal dianions, stabilized by main group elements. Three cases can thus be considered: the gem dilithio derivative, for which the two substituents at C are neutral, the ylidiide derivatives, for which one substituent is neutral while the other is charged, and finally the geminal bisylides, for which the two substituents are positively charged. In this review the syntheses and electronic structures of the geminal dianions are presented, followed by the studies dedicated to their reactivity toward organic substrates and finally to their coordination chemistry and applications. Reactivity of doubleylides towards organic compounds. 4.4. Coordination chemistry of double ylides to metallic species. 4.4.1. Coordination to Group 2 Metals. 4.4.2. Coordination to Actinides: Uranium Complexes 4.4.3. Coordination to Group 4 Metals: Zirconium Complexes 4.4.4. Coordination to Group 6 Metals: Tungsten Complexes 4.4.5. Coordination to Group 7 Metals: Manganese and Rhenium Complexes 4.4.6. Coordination to Group 8 Metals: Iron Complexes 4.4.7. Coordination to Group 9 Metals: Rhodium and Iridium Complexes 4.4.8. Coordination to Group 10 Metals 4.4.9. Coordination to Group 11 (Coinage) Metals 4.4.10. Coordination to Group 12 Metals 4.5. Reactivity of double ylides towards main group elements. 4.5.1. Group 13 4.5.2. Group 14 4.5.3. Group 15 4.5.4. Group 16 4.5.5. Group 17 4.6. Carbodicarbenes 4.6.1. Synthesis 4.6.2. Reactivity 4.6.3. Coordination chemistry 4.6.4. Reactivity with main group elements 5. Conclusion 6. Acknowledgements 7. References lengths in complexes [(7)Mg(THF)] 2 and [(14)Mg(THF) 3 ] at 2.156(5)Å and 2.113(4)Å resp. are as expectedly significantly shorter than the ones measured in the dimers [(6a)Mg] 2 and [(10)Mg] 2 at 2.225(2)Å (av.) and 2.267(3)Å (av.). Electronic structureThe question of the nature of the bond between the AE metal and C was addressed. Harder et al.performed a DFT study first on models of [(6a)Ca] 2 and [(6f)Ca] where H atoms were considered in place of the real phenyl groups at P and groups (SiMe 3 and Ar resp.) at N. 49 In the case of the monomeric complex [(6f)Ca], the solvent molecules were not taken into account. Not surprising in light of the difference of electronegativity of the elements, the charge at C varied between -1.623 (monomer) and -1.847 (dimer) whereas charge at Ca varied between +1.760 (monomer) and +1.821 (dimer). The Ca-C bond was thus described as highly ionic. The calculations with the full dimeric system were carried out, and a slightly reduced charge was calculated at C (-1.778). The NPA charges were also compared to the ones in neutral 6aH 2 and the [Ca(6aH) 2 ] complex. Expectedly the charge at C goes from -1.079 to -1.409 to -1.778 (in 6aH2, [Ca(6aH) 2 ], [Ca(6a)] 2 resp.). The charge at N also increases (-1.474 to -1.580 to -1.665 resp.) upon deprotonation at C. Conversely, the charge at P varies but to a small extent (+1.747 to +1.727 to +1.7...

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Bent and Linear Forms of the (μ‐Oxo)bis[trichloroferrate(III)] Dianion: An Intermolecular Effect − Structural, Electronic and Magnetic Properties

et al. 2003

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We have analyzed the great diversity of Fe−O−Fe angles, 140−180°, found in the X‐ray structures of the (μ‐oxo)bis[trichloroferrate(III)] dianion [Cl3FeOFeCl3]2− from both experimental and theoretical points of view. Theoretical calculations show that only the linear isomer is found as a minimum on the potential energy surface. Detailed analysis of the crystal packing indicates that the angular form is due to attractive intermolecular interactions. Analysis of a selected reduced set of the 45 crystal structures retrieved from the Cambridge Structural Database allowed us to classify the bending of the [Cl3FeOFeCl3]2− dianion in three categories, depending on the balance and strength of the intermolecular O···H−X contacts. A crystal diffraction study on the bis(benzyltrimethylammonium) salt has shown both bent (144.6°) and linear (180°) forms of the (μ‐oxo)bis[trichloroferrate(III)] dianion. The magnetic susceptibility of this compound has been fitted by assuming two equally weighted contributions (Jang and Jlin) of the two forms, considering Jang − Jlin estimated by theoretical calculations. The obtained Jang and Jlin of −117 and −133 cm−1 respectively, agree well with B3LYP results. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Oxidative Coupling of the Selenolate Functions in (C₆H₅)₃PC(Se)P(C₆H₅)₃: Crystal Structure of {[(C₆H₅)₃P]₂CSe}Fe₂OCl·4CH₂Cl₂ Containing a Linear FeOFe Axis

Abstract: The complete manuscript of this communication appears in: Angew. Chem. Suppl. 1983, 169. DOI:

Cited by 14 publications

References 5 publications

Synthesis and Se−Se Bond Breaking of Polyselenides Containing Pendant Diphosphine Complexes of Manganese(I)

Synthesis and Se−Se Bond Breaking of Polyselenides Containing Pendant Diphosphine Complexes of Manganese(I)

Geminal Dianions Stabilized by Main Group Elements

Bent and Linear Forms of the (μ‐Oxo)bis[trichloroferrate(III)] Dianion: An Intermolecular Effect − Structural, Electronic and Magnetic Properties

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