ChemInform Abstract: A NEW SYNTHESIS OF METHYLENEBIS(DIORGANYLPHOSPHINES) AND AN UNUSUAL DECOMPOSITION BY ALKALI METALS

Appel, Rolf; Geisler, Klaus; Schoeler, H. F.

doi:10.1002/chin.197916290

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“…Chlorinated CDPs represent an attractive organic synthon that offer structural diversity through reaction with the appropriate nucleophiles such as secondary amines. This appealing strategy was introduced by Appel in 1979 with the synthesis of the bis(chlorodiphenylphosphoranediyl)methane (PPh 2 Cl) 2 C ( 168 ) in nearly quantitative yield (90%) from an excess of CCl 4 and (Ph 2 P) 2 CH-SiMe 3 . , Compound 168 was fully characterized by 1 H and 31 P NMR, mass spectrum, and its chemical reactivity vs HCl and alcohols, giving rise to the phosphonium salt [ 168 -H][Cl] and the dioxide ( 169) , respectively (Scheme ). The utility of chlorinated CDPs as organic synthons was then demonstrated by Appel and co-workers in 1981, when they reported on the aminolysis reaction of C(PPh 2 Cl 2 ) 2 ( 168 ) with secondary amines HNR 2 (R = Me, Et, n Pr, and n Bu), leading to the phosphonium salts [(R 2 N)Ph 2 PC(H)-PPh 2 NR 2 ][Cl] ([ 170a – d ][Cl] in Scheme ).…”

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

confidence: 99%

“…Chlorinated CDPs represent an attractive organic synthon that offer structural diversity through reaction with the appropriate nucleophiles such as secondary amines. This appealing strategy was introduced by Appel in 1979 with the synthesis of the bis(chlorodiphenylphosphoranediyl)methane (PPh 2 Cl) 2 C(168) in nearly quantitative yield (90%) from an excess of CCl 4 and (Ph 2 P) 2 CH-SiMe 3 287,288. Compound 168 was fully characterized by 1 H and 31 P NMR, mass spectrum and its chemical reactivity vs HCl and alco-CDPs as reported by Wheatley,262,263 Zink,264 and Schmidbaur276,277,280 having P-C-P angles ranging from 143.8(6)°2 63 in 130 to 116.7(7)°2 77 in the case of the 6-membered cyclic CDP 157.…”

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“…Attempts to prepare the analogous hexamethylcarbodiphosphorane 135 from [Me 3 PC(Cl)-PMe 3 ][Cl] salt286 failed.Chlorinated CDPs represent an attractive organic synthon that offer structural diversity through reaction with the appropriate nucleophiles such as secondary amines. This appealing strategy was introduced by Appel in 1979 with the synthesis of the bis(chlorodiphenylphosphoranediyl)methane (PPh 2 Cl) 2 C (168) in nearly quantitative yield (90%) from an excess of CCl 4 and (Ph 2 P) 2 CH-SiMe 3 287,288. Compound 168 was fully characterized by 1 H and 31 P NMR, mass spectrum, and its chemical reactivity vs HCl and alcohols, giving rise to the phosphonium salt[168-H][Cl] and the dioxide(169), respectively (Scheme 146).…”

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

confidence: 99%

“…Chlorinated CDPs represent an attractive organic synthon that offer structural diversity through reaction with the appropriate nucleophiles such as secondary amines. This appealing strategy was introduced by Appel in 1979 with the synthesis of the bis(chlorodiphenylphosphoranediyl)methane (PPh 2 Cl) 2 C(168) in nearly quantitative yield (90%) from an excess of CCl 4 and (Ph 2 P) 2 CH-SiMe 3 287,288. Compound 168 was fully characterized by 1 H and 31 P NMR, mass spectrum and its chemical reactivity vs HCl and alco-CDPs as reported by Wheatley,262,263 Zink,264 and Schmidbaur276,277,280 having P-C-P angles ranging from 143.8(6)°2 63 in 130 to 116.7(7)°2 77 in the case of the 6-membered cyclic CDP 157.…”

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