dr hab. inż. Łukasz Ponikiewski | Gdańsk University of Technology

This study was focused on the activation of the C[double bond, length as m-dash]P bond via reactions of Ph2C[double bond, length as m-dash]P-PtBu2 (1) with 1,6-hexanediol and selected dithiols (1,4-butanedithiol, 1,4-benzenedithiol and 1,4-benzenedimethanethiol). These reactions proceed according to a 1,2-addition mechanism, providing new compounds with formulas {(Ph)2(H)C-P-PtBu2}{μ2-(O-(CH2)6-O)}{tBu2P-P-C(H)(Ph)2} (2), {(Ph)2(H)C-P-PtBu2}{μ2-(S-(CH2)4-S)}{tBu2P-P-C(H)(Ph)2}...

Synthesis and modifications of new chiral phospholene-based scaffolds are described. The construction of base molecules was accomplished via McCormack synthesis. Separation of single P-epimers was accomplished with column chromatography on silica gel.

We synthesized phosphanylphosphaalkenes (biph)2C=P-P(tBu)2 (2), Ph2CvP-P(NEt2)2 (3), and (biph)2CvP-P(NEt2)2 (4). The diaminophosphanyl derivatives reversibly dimerize head-to-head and react with a ruthenium complex, leading to P–P bond activation and the formation of a bridging phospaalkene complex under mild conditions.

Asimplemethodforthesynthesisof3-arylbenzophospholeoxidesunderSuzuki−Miyauracouplingconditionshasbeenpresented.Itemploysbenzophosphol-3-yltriflatestartingmaterialswhich,priortoourwork,hadnotbeenusedforthesynthesisof3-arylbenzophospholeoxides.Thereactionsproceedover24handprovidealibraryof3-arylbenzophospholeoxides.Thesyntheticaccesstothebenzophosphol-3-yltriflateshasbeenimproved.Thepreliminaryphotophysicalpropertiesofsome3-arylbenzophospholeoxideshavebeeninvestigatedbyabsorptionandemissionmeasurements.Thetheoreticalcalculationswereperformedtoestablishstructure−propertyrelationships.

The reactivities of two selected phosphanylphosphaalkenes, Ph2C=P-PtBu2 (1a) and (p-MeO-Ph)2C=P-PtBu2 (1b), toward CuCl, AgCl and (tht)AuCl (tht = tetrahydrothiophene) were investigated. As a result, new phosphanylphosphaalkene dimeric and monomeric complexes were formed (Cu and Ag dimeric and Au monomeric). All obtained products were air and moisture stable and light insensitive.