Metal Phosphinylides and Phosphinothioylides. VII. The Structure of [Ph2PX]M (X=O, S) in Solution and Their Disproportionation

Goda, Koshiro; Gomi, Hideyuki; Yoshifuji, Masaaki; Inamoto, Naoki

doi:10.1246/bcsj.50.545

Cited by 18 publications

(11 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Diphenylphosphinites of the alkali metals have been well-known for many years, and 31 P NMR studies supported already half a century ago that the metals are bound to the oxygen atom rather than to the phosphorus atom . Several procedures provide suitable access to these phosphinites such as the reaction of neat triphenylphosphane oxide or benzyldiphenylphosphane oxide with LiH and NaH at high temperatures or metalation of diphenylphosphane oxide with butyllithium .…”

Section: Introductionmentioning

confidence: 99%

Influence of 18-Crown-6 Ether Coordination on the Catalytic Activity of Potassium and Calcium Diarylphosphinites in Hydrophosphorylation Reactions

et al. 2017

View full text Add to dashboard Cite

The addition of 18-crown-6 ether (1,4,7,10,13,16-hexaoxacyclooctadecane) to tetranuclear [(thf)K(OPAryl)] and [(thf)Ca(OPAryl)] yields the corresponding mononuclear complexes [(18C6)K(OPAryl)] [Aryl = Ph (1a), Mes (1b)] and [(18C6)Ca(OPAryl)] [Aryl = Ph (2a), Mes (2b)]. The metathesis reaction of [(thf)K(OPAryl)] with CaI yields the calciate [KCa(thf){OPMes}]. The addition of dimesitylphosphane oxide and crystallization from a hexane solution gives [KCa{OPMes}{MesP(O)H}] (3). The complexes [(thf)K(OPMes)], [(thf)Ca(OPMes)], 1b, 2b, and the calciate 3 are tested as catalysts in the hydrophosphorylation of isopropylisocyanate with dimesitylphosphane oxide, quantitatively yielding N-isopropyl(dimesitylphosphoryl)formamide. The potassium complexes are more efficient catalysts than the calcium congeners, and coordination of 18-crown-6 decelerates the catalytic conversion.

show abstract

Section: Introductionmentioning

confidence: 99%

Influence of 18-Crown-6 Ether Coordination on the Catalytic Activity of Potassium and Calcium Diarylphosphinites in Hydrophosphorylation Reactions

et al. 2017

View full text Add to dashboard Cite

show abstract

“…26 Reduction of diphenylphosphinic and -thiophosphinic chloride with sodium or magnesium as well as metalation of diphenylphosphane oxide and sulfide also yielded the corresponding diphenylchalcogenophosphinites. 27 These Ph 2 PE − anions show a diverse coordination behavior as terminal or bridging ligands via the chalcogen atom or as bridging ligands via the phosphorus and chalcogen bases. The last mentioned binding mode was found in [(tmeda)LiSePPh 2 ] 2 .…”

Section: ■ Introductionmentioning

confidence: 99%

“…Bildstein and Sladky investigated the oxidation of LiPPh 2 with chalcogens in THF and found a linear correlation between the chemical 31 P NMR shift and the Pauling electronegativity of the chalcogen for Ph 2 PE-Li (diphenylchalcogenophosphinites) and Ph 2 PE 2 Li (diphenyldichalcogenophosphinates) . Reduction of diphenylphosphinic and -thiophosphinic chloride with sodium or magnesium as well as metalation of diphenylphosphane oxide and sulfide also yielded the corresponding diphenylchalcogenophosphinites . These Ph 2 PE – anions show a diverse coordination behavior as terminal or bridging ligands via the chalcogen atom or as bridging ligands via the phosphorus and chalcogen bases.…”

Section: Introductionmentioning

confidence: 99%

Oxidation Products of Calcium and Strontium Bis(diphenylphosphanide)

et al. 2012

View full text Add to dashboard Cite

The tetrahydrofuran adducts [(thf)(4)M(PPh(2))(2)] (M = Ca, Sr) are air sensitive and can easily be oxidized by chalcogens. Metalation of diphenylphosphane oxide, diphenylphosphinic acid, and diphenyldithiophosphinic acid as well as salt metathetical approaches of the potassium salts with MI(2) allow the synthesis of [(thf)(4)Ca(OPPh(2))(2)] (1), [(dmso)(2)Ca(O(2)PPh(2))(2)] (2), [(thf)(3)Ca(O(2)PPh(2))I](2) (3), [(thf)(3)Ca(S(2)PPh(2))(2)] (4), [(thf)(2)Ca(Se(2)PPh(2))(2)] (5), [(thf)(3)Sr(S(2)PPh(2))(2)] (6), [(thf)(3)Sr(Se(2)PPh(2))(2)] (7), and [(thf)(2)Ca(O(2)PPh(2))(S(2)PPh(2))](2) (8), respectively. The diphenylphosphinite anion in 1 contains a phosphorus atom in a trigonal pyramidal environment and binds terminally via the oxygen atom to calcium. The diphenylphosphinate anions act as bridging ligands leading to polymeric structures of calcium bis(diphenylphosphinates). Therefore strong Lewis bases such as dimethylsulfoxide (dmso) are required to recrystallize this complex yielding chain-like 2. The chain structure can also be cut into smaller units by ligands which avoid bridging positions such as iodide and diphenyldithiophosphinate (3 and 8, respectively). In general, diphenyldithio- and -diselenophosphinate anions act as terminal ligands and allow the isolation of mononuclear complexes 4 to 7. In these molecules the alkaline earth metals show coordination numbers of six (5) and seven (4, 6, and 7).

show abstract

“…On the other hand, in the reaction of compound 6a with sodium in toluene, the formation of sodium diphenylphosphinite ( 8b’ ) or diphenylphosphido anion ( 19b’ ) was observed, depending on the amount of sodium used in this reaction [ 90 ]. Inamoto and co-workers conducted several experiments where electrophile 6a was treated by alkali metals and metal salts in THF [ 91 ]. Sasaki et al described the reduction of electrophile 6a with SmI 2 , at room temperature in THF.…”

Section: The Diphosphine Dioxidesmentioning

confidence: 99%

The Synthesis of Hypodiphosphoric Acid and Derivatives with P-P Bond, including Esters and Diphosphine Dioxides: A Review

Nycz¹

2021

Molecules

View full text Add to dashboard Cite

The synthesis of hypodiphosphoric acid and its related compounds began in 1877, but no summary of the synthetic efforts has been reported. This review includes published papers related to the molecules containing the >P(=O)-P(=O)< fragment, which notably resembles the structure of the >P(=O)-O-P(=O)< moiety, the essential building block of many important molecules found in nature and in the field of medicinal chemistry. This review covers the strategies related to the synthesis of hypodiphosphoric acid (former name hypophosphoric acid), its ester form, and diphosphine dioxides. Finally, some properties and applications of these structures studied during this period are presented.

show abstract

Metal Phosphinylides and Phosphinothioylides. VII. The Structure of [Ph2PX]M (X=O, S) in Solution and Their Disproportionation

Abstract: The species [Ph2PO]M in THF were found to exist as Ph2P–O–M by 31P-NMR, and [Ph2PS]MgCl as Ph2P–S–MgCl by Raman spectrum. The species [Ph2PS]M undergo easy disproportionation by heating.

Cited by 18 publications

References 9 publications

Influence of 18-Crown-6 Ether Coordination on the Catalytic Activity of Potassium and Calcium Diarylphosphinites in Hydrophosphorylation Reactions

Influence of 18-Crown-6 Ether Coordination on the Catalytic Activity of Potassium and Calcium Diarylphosphinites in Hydrophosphorylation Reactions

Oxidation Products of Calcium and Strontium Bis(diphenylphosphanide)

The Synthesis of Hypodiphosphoric Acid and Derivatives with P-P Bond, including Esters and Diphosphine Dioxides: A Review

Contact Info

Product

Resources

About