Formation and Crystal Structure of the Salt (IC(PPh3)2)2I[I3]·(I2)2 with a new Polyiodide Chain

Petz, Wolfgang; Heimann, Samuel; Öxler, Florian; Neumüller, Bernhard

doi:10.1002/zaac.200600311

Cited by 16 publications

(7 citation statements)

References 24 publications

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“…Ar elated elongation is also recorded in going from NHC-Cl + (1.686 ) [34] to 1Cl + + (1.775 ), [24] from NHC-Br + (1.854 ) [34] to 1Br + + (1.939(2) ), and from NHC-I + (2.042 ) [35] to 1I + + (2.134 ). [36] The mean P-C(1) distance of the two independentm olecules in 1F + + amountst o1 .716 a nd is slightly shorter than in 1Cl + + (1.722 ), which may be ah int for in-creasedC -P back-bonding. For the P-C-P angle, an unusually large value of about 1408 was recorded, far from the typical angles in other type Ia ddition compounds.R elatively weak bridgese xist between phenyl protons and the atoms Fo rB r. One run produced crystals with strongly disordered Fa toms, resultingi napyramidal arrangement at C(1) (1F + + -S); the molecular structure is depicted in the Supporting information ( Figure 1S).…”

Section: Resultsmentioning

confidence: 91%

Proton Affinities of Cationic Carbone Adducts [AC(PPh₃)₂]⁺(A=Halogen, Hydrogen, Methyl) and Unusual Electronic Structures of the Cations and Dications [AC(H)(PPh₃)₂]²⁺

Petz

Kuzu

Frenking

et al. 2016

Chemistry A European J

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This work reports the syntheses and the first crystal structures of the cationic carbone adducts [FC(PPh3 )2 ](+) and [BrC(PPh3 )2 ](+) and the protonated dication [FC(H)(PPh3 )2 ](2+) , which are derived from the carbone C(PPh3 )2 . Quantum chemical calculations and bonding analyses were carried out for the series of cations [AC(PPh3 )2 ](+) and dications [AC(H)(PPh3 )2 ](2+) , where A=H, Me, F, Cl, Br, I. The bonding analysis suggests that the cations are best described as phosphane complexes L→(CA)(+) ←L (L=PPh3 ), which are related to the neutral borylene adducts L→(BA)←L (L=cyclic carbene; A=H, aryl) that were recently isolated. The carbone adducts [AC(PPh3 )2 ](+) possess a π electron lone pair at carbon and they can easily be protonated to the dications [AC(H)(PPh3 )2 ](2+) . The calculations of the dications indicate that the molecules are best represented as complexes L→(CHA)(2+) ←L (L=PPh3 ) where a carbene dication is stabilized by the ligands. The central carbon atom in the cations and even in the dications carries a negative partial charge, which is larger than the negative charge at fluorine. There is also the peculiar situation in which the carbon-fluorine bonds in [FC(PPh3 )2 ](+) and [FC(H)(PPh3 )2 ](2+) exhibit the expected polarity with the negative end at fluorine, but the carbon atom has a larger negative charge than fluorine. Given the similarity of carbodiphosphorane C(PPh3 )2 and carbodicarbene C(NHC)2 , we expect that analogous compounds [AC(NHC)2 ](+) and [AC(H)(NHC)2 ](2+) with similar features as [AC(PPh3 )2 ](+) and [AC(H)(PPh3 )2 ](2+) can be isolated.

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Section: Resultsmentioning

confidence: 91%

Proton Affinities of Cationic Carbone Adducts [AC(PPh₃)₂]⁺(A=Halogen, Hydrogen, Methyl) and Unusual Electronic Structures of the Cations and Dications [AC(H)(PPh₃)₂]²⁺

Petz

Kuzu

Frenking

et al. 2016

Chemistry A European J

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“…Oxidation reactions of CDP 130 were explored by Petz , and Schmidbaur . The first report covering the oxidation of 130 by elemental iodine to form 130 -I was published by Schmidbaur in 1985 (Scheme ).…”

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

confidence: 99%

“…Very recently, Petz reported an alternative way of synthesis for the cation 130 -I in presence of iodine and methyl iodide. The salt [ 130 -I][I 3 ] was crystallized in 10%, allowing to confirm its structure by XRD analysis …”

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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“…These compounds exhibited unusually long C−X bond lengths as a consequence of the repulsion between the lone pairs at the halogen and the carbon atom. 18 Similarly, 3 features a C−I bond of 2.145(4) Å, which is slightly longer than that in A-I (2.134 Å) 19 and is in the range of C−I bonds at a carbanionic carbon center (carbenoids). 20 In the crystal structure of 3, the iodo substituents exhibits a weak interaction with the I 3 − and I − counteranions, respectively.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Cationic Phosphorus Compounds Based on a Bis(1-piperidinyl)-Substituted Carbodiphosphorane: Syntheses, Structures, and C_sp³–H Activation

et al. 2020

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The use of the bis(1-piperidinyl)-substituted carbodiphosphorane (Ph2(Pip)P)2C (1) as an NCN ligand for the stabilization of phosphorus cations was studied. A simple ligand for halide exchange allowed the synthesis and isolation of a series of phosphorus monocations of the type [1-PR2]+ (with R = Cl, Br, I, CyCl, Ph). These cations exhibit characteristic NMR and structural properties which nicely correlate with the charge at the central phosphorus atom and the interaction between the ligand and the PR2 moiety. Halide abstraction from the monocations does not result in isolable dicationic compounds but in an unexpected intramolecular Csp3 –H activation in the piperidinyl group. DFT studies show that the selective activation of the CH2 group next to the nitrogen atom instead of a CH group at the phenyl substituents proceeds via an iminium intermediate formed by hydride transfer from the carbon atom to the cationic phosphorus center. This observation clearly demonstrates the pronounced π acidity of the dicationic phosphorus species in comparison to compounds with a further π-donor substituent.

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Formation and Crystal Structure of the Salt (IC(PPh₃)₂)₂I[I₃]·(I₂)₂ with a new Polyiodide Chain

Cited by 16 publications

References 24 publications

Proton Affinities of Cationic Carbone Adducts [AC(PPh₃)₂]⁺(A=Halogen, Hydrogen, Methyl) and Unusual Electronic Structures of the Cations and Dications [AC(H)(PPh₃)₂]²⁺

Proton Affinities of Cationic Carbone Adducts [AC(PPh₃)₂]⁺(A=Halogen, Hydrogen, Methyl) and Unusual Electronic Structures of the Cations and Dications [AC(H)(PPh₃)₂]²⁺

Geminal Dianions Stabilized by Main Group Elements

Cationic Phosphorus Compounds Based on a Bis(1-piperidinyl)-Substituted Carbodiphosphorane: Syntheses, Structures, and C_sp³–H Activation

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Formation and Crystal Structure of the Salt (IC(PPh3)2)2I[I3]·(I2)2 with a new Polyiodide Chain

Cited by 16 publications

References 24 publications

Proton Affinities of Cationic Carbone Adducts [AC(PPh3)2]+(A=Halogen, Hydrogen, Methyl) and Unusual Electronic Structures of the Cations and Dications [AC(H)(PPh3)2]2+

Proton Affinities of Cationic Carbone Adducts [AC(PPh3)2]+(A=Halogen, Hydrogen, Methyl) and Unusual Electronic Structures of the Cations and Dications [AC(H)(PPh3)2]2+

Geminal Dianions Stabilized by Main Group Elements

Cationic Phosphorus Compounds Based on a Bis(1-piperidinyl)-Substituted Carbodiphosphorane: Syntheses, Structures, and Csp3–H Activation

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Formation and Crystal Structure of the Salt (IC(PPh₃)₂)₂I[I₃]·(I₂)₂ with a new Polyiodide Chain

Proton Affinities of Cationic Carbone Adducts [AC(PPh₃)₂]⁺(A=Halogen, Hydrogen, Methyl) and Unusual Electronic Structures of the Cations and Dications [AC(H)(PPh₃)₂]²⁺

Proton Affinities of Cationic Carbone Adducts [AC(PPh₃)₂]⁺(A=Halogen, Hydrogen, Methyl) and Unusual Electronic Structures of the Cations and Dications [AC(H)(PPh₃)₂]²⁺

Cationic Phosphorus Compounds Based on a Bis(1-piperidinyl)-Substituted Carbodiphosphorane: Syntheses, Structures, and C_sp³–H Activation