100281-28-5Relevant articles and documents
Phosphorus centers of different hybridization in phosphaalkene-substituted phospholes
Oeberg, Elisabet,Orthaber, Andreas,Lescop, Christophe,Reau, Regis,Hissler, Muriel,Ott, Sascha
supporting information, p. 8421 - 8432 (2014/07/08)
Phosphole-substituted phosphaalkenes (PPAs) of the general formula Mes P=C(CH3)-(C4H2P(Ph))-R 5a-c (Mes=2,4,6-tBu 3Ph; R=2-pyridyl (a), 2-thienyl (b), phenyl (c)) have been prepared from octa-1,7-diyne-substituted phosphaalkenes by utilizing the Fagan-Nugent route. The presence of two differently hybridized phosphorus centers (σ2,λ3 and σ3, λ3) in 5 offers the possibility to selectively tune the HOMO-LUMO gap of the compounds by utilizing the different reactivity of the two phosphorus heteroatoms. Oxidation of 5a-c by sulfur proceeds exclusively at the σ3,λ3-phosphorus atom, thus giving rise to the corresponding thioxophospholes 6a-c. Similarly, 5a is selectively coordinated by AuCl at the σ3,λ3-phosphorus atom. Subsequent second AuCl coordination at the σ2, λ3-phosphorus heteroatom results in a dimetallic species that is characterized by a gold-gold interaction that provokes a change in π conjugation. Spectroscopic, electrochemical, and theoretical investigations show that the phosphaalkene and the phosphole both have a sizable impact on the electronic properties of the compounds. The presence of the phosphaalkene unit induces a decrease of the HOMO-LUMO gap relative to reference phosphole-containing π systems that lack a P=C substituent.
Preparation and properties of kinetically stabilized phosphaethene derivatives carrying the methylsulfanyl group
Ito, Shigekazu,Kimura, Shigeo,Yoshifuji, Masaaki
, p. 405 - 412 (2007/10/03)
1-Methylsulfanyl-2-(2,4,6-tri-t-butylphenyl)-2-phosphaethenyllithiums, prepared from (Z)-2-bromo-2-methylsulfanyl-1-(2,4,6-tri-t-butylphenyl)-1-phosphaethene, displayed an E/Z isomerization upon warming to room temperature. The copper-mediated coupling reaction afforded (Z,Z)-2,3-bis(methylsulfanyl)-1,4-diphosphabuta-1,3-diene. The reaction of the phosphaethenyllithiums with dimethyl disulfide and iodomethane gave the corresponding bis(methylsulfanyl)phosphaethene and a methylated E-isomer, respectively. On the other hand, the latter methylated Z-isomer was alternatively prepared from (Z)-2-bromo-1-(2,4,6-tri-t-butylphenyl)-1-phosphapropene. Both methylated E- and Z-isomers were allowed to react with W(CO)5(thf) to give the corresponding pentacarbonyltungsten(0) complexes, either of which was deprotonated to give the 3-phospha-2-propenyllithium derivative leading to the formation of a homocoupled (Z,Z)- 1,6-diphosphahexa-1,5-diene complex. Some key compounds were analyzed by X-ray crystallography, revealing the effect of the methylsulfanyl group on the structures. A straightforward preparation of 1-(2,4,6-tri-t-butylphenyl)-1-phosphaallene as well as its carbonyltungsten(0) complex is also described.
SYNTHESE UND REAKTIONEN DER 2,4,6-TRI-TERT-BUTYLPHENYLDIHALOGENMETHYLENPHOSPHANE1
Appel, Rolf,Casser, Carl,Immenkeppel, Michael
, p. 3551 - 3554 (2007/10/02)
The synthesis of dihalogenated phosphaalkanes 2a,b is reported.After metallation with n-BuLi they could be substituted by halogenated compounds.
