Reductive Ring Opening of a Cyclo-Tri(phosphonio)methanide Dication to a Phosphanylcarbodiphosphorane: <i>In Situ</i> UV-Vis Spectroelectrochemistry and Gold Coordination

Yogendra, Sivathmeehan; Schulz, Stephen; Hennersdorf, Felix; Kumar, S R Sarath; Fischer, Roland; Weigand, Jan J.

doi:10.1021/acs.organomet.7b00597

Cited by 16 publications

(23 citation statements)

References 38 publications

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“…Both Pd and Au coordinate geminally at C1 of CDC with bond distance of 2.095(3) and 2.113(3) Å, respectively (Figure S5). The observed Au‐carbone bond length is comparable to literature values for gem ‐aurate supported by carbones (2.078 to 2.127 Å) [11a, 12b,c, 13a,c, 14, 15] . The bond angle of 84.97(10)° for Au‐C1‐Pd is slightly smaller than observed in 1 (89.25°).…”

Section: Resultssupporting

confidence: 81%

“…There are currently an umber of speciese xhibiting gem-bimetallic interactions bearing C 0 . [11][12][13] However,t he selections and flexibility of putting different metals are very limited, as linear gold or silver complexes with less steric congestion were chosen to access gem-bimetallic complexes. [11] More importantly,t he majority of examples are restricted to the non-allenic motif such as C(PPh 3 ) 2 .S pecifically,t here is al ack of any experimental evidencef or CDCs in regardt ot heir predicted secondary binding behavior.…”

Section: Introductionmentioning

confidence: 99%

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Carbodicarbene: geminal‐Bimetallic Coordination in Selective Manner

Au‐Yeung

Xiao

Shih

et al. 2020

Chemistry A European J

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The reaction of Pd(OAc) 2 with free carbodicarbene (CDC) generates aP da cetate trinuclear complex 1 via intramolecular C(sp 3)ÀHb ond activation at one of the CDC methyl side arms.T he solid structure of 1 reveals the capability of CDC to facilitate ad ouble dative bond with two palladium centers in geminal fashion. This is attributed to the chelating mode of CDC, which can frustrate pconjugation within the CDC framework. Such effect maybe also amplified by ligand-ligand interaction. The formation of other gem-bimetallic PdÀPd,P d ÀAu, and NiÀAu provides further structurale videncef or this proof-of-concept in selective installation. Structurala nalysisi ss upported by computational calculations based on state-of-theart energy decompositiona nalysis (EDA) in conjunction with natural orbitals for chemicalv alence (NOCV)m ethod.

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Section: Resultssupporting

confidence: 81%

Section: Introductionmentioning

confidence: 99%

Carbodicarbene: geminal‐Bimetallic Coordination in Selective Manner

Au‐Yeung

Xiao

Shih

et al. 2020

Chemistry A European J

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“…309 The observed regioselectivity in 229b, in which the imine is now directly Recently, Weigand reported the 2ereduction of the cyclotri(phosphonio)methanide [234][OTf] 2 that resulted in the synthesis of the acyclic CDP 235 in 81% yield via ring opening process. 310…”

Section: Synthesis Of Carbodiphosphoranes and Other Related Heteroatom-stabilized Bis(ylide)smentioning

confidence: 99%

“…From these two precursors, the 2 e ─ oxidation was carried out with HNO 3 or the combination of I 2 and TlOTf to efficiently yield complexes [457] Meticulous control of the reaction stoichiometry allowed the access to the mono-, di-and triauration products with the potentially 6 electrons donor phosphinocarbodiphosphorane 235 described by Weigand. 310 The respective complexes 459-461 were isolated in excellent yields and appropriately char-…”

Section: Coordination Chemistry Of Type II Geminal Dianionsmentioning

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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“…In case of the dication, a further amino substituent at the phosphorus atom was required to balance its electron deficiency through additional π donation from N to P. Dications with other substituents were found to be highly reactive, and the trication could only be isolated in the form of a few crystals. In addition, diphenyl-substituted cations based on CDP A have been reported by Weigand and co-workers and used for the preparation of very Lewis acidic phosphonium dications …”

Section: Introductionmentioning

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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Reductive Ring Opening of a Cyclo-Tri(phosphonio)methanide Dication to a Phosphanylcarbodiphosphorane: In Situ UV-Vis Spectroelectrochemistry and Gold Coordination

Cited by 16 publications

References 38 publications

Carbodicarbene: geminal‐Bimetallic Coordination in Selective Manner

Carbodicarbene: geminal‐Bimetallic Coordination in Selective Manner

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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Reductive Ring Opening of a Cyclo-Tri(phosphonio)methanide Dication to a Phosphanylcarbodiphosphorane: In Situ UV-Vis Spectroelectrochemistry and Gold Coordination

Cited by 16 publications

References 38 publications

Carbodicarbene: geminal‐Bimetallic Coordination in Selective Manner

Carbodicarbene: geminal‐Bimetallic Coordination in Selective Manner

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