Two complementary approaches for the synthesis and isolation of stable phosphanylphosphaalkenes

Abstract

Phospha-Wittig (phosphanylphosphinidene titanium(IV) complex) and phospha-Peterson (lithiated diphosphane) reactions were used to obtain phosphanylphosphaalkenes with the general formula XYC=P-PtBu2 (X = alkyl, aryl group or H; Y = alkyl or...

From phosphanylphosphaalkenes to coordination copper and silver polymers containing P–P bonds

“…These lengths fall within the range of a single P-P bond and are comparable to those observed in 1 (2.2173(8) Å). 34 The C-P bond lengths, 1.8953(13) Å in 3a and 1.888(3) Å in 3c, best describe P-C single bonds and are comparable to those observed in naphtho[1,8-cd]1,2-dithioleiso-propylphosphine [NapS 2 PiPr] (1.87(1) Å, 1.86(6) Å, 1.89(1) Å) and 2,3aβ,8β-triphenyl-3a,8-dihydro-1-thia-8a-phosphacyclopenta[a]indene-P-( pentacarbonyl)tungsten (1.879(7) Å). 51,52 In 3a, 3b, and 3c, there are two stereogenic centers: P1 and P1A atoms.…”

“…20,31,32 A much smaller part of this family is the phosphanylphosphaalkenes, characterized as systems bearing CvP-P bonds. 33,34 The additional phosphorus atom decreases the polarity of the CvP bond stabilizing the molecule. Moreover, the additional phosphorus atom now becomes the most electropositive atom in the phosphanylphosphaalkene.…”

Activation of the CP bond in phosphanylphosphaalkenes (CP–P bond system) in the reaction with nucleophilic reagents: MeLi, nBuLi and tBuLi

“…(biph)(H)C P–P t Bu 2 and ( p -Me 2 N–C 6 H 4 )(H)C P–P t Bu 2 were prepared according to procedure in the literature. 32 MeLi, n BuLi and t BuLi were commercially purchased.…”

“…26 Changing the substituent on the phosphorus atom with a phosphanyl group leads to the formation of phosphanylphosphaalkene (C]P-P). [27][28][29][30][31][32] These diphosphorus analogs are a considerable and lesser known group of compounds, and their reactivity is practically unknown. Our main goal was to perform the rst step of anionic polymerization in solution (tetrahydrofuran, THF) at room temperature; for this purpose, we chose (biph)(H)C]P-PtBu 2 (1), (3,5-tBu 2 C 6 H 3 )(H)C]P-PtBu 2 (3) and (p-Me 2 N-C 6 H 4 )(H)C] P-PtBu 2 (4) containing an aldehyde derivative.…”

Group 11 complexes with a phosphanylphosphaalkene ligand: preparation and stability study

“…For comparison, the P–P and CP distances observed in the noncoordinated phosphanylphosphaalkenes 1a and 1b were 2.2121(7) Å, 2.2115(12) Å, 1.6983(19) Å and 1.707(3) Å, respectively. 21 The Cu–Cu distances in Cu1 and Cu2 were 3.008(2) Å and 3.0356(5) Å, indicating a lack of interactions between the copper atoms.…”