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This article discusses the synthesis of a new P-chiral phospholene core-based ligand called LemPhos. The authors propose a method using a chiral diene to create diastereomers that are easier to separate, allowing for the production of P-chiral ligands. The ligands are synthesized and characterized, and their application as catalysts in asymmetric hydrogenation reactions is explored. The document also includes experimental procedures and spectroscopic data for the synthesized compounds. The research is dedicated to the memory of Stanisław Lem, a renowned science-fiction writer. [Extracted from the article]

This study was focused on the activation of the C＝P bond via reactions of Ph2C＝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} (3a), {(Ph)2(H)C-P-PtBu2}{μ2-(S-C6H4-S)}{tBu2P-P-C(H)(Ph)2} (3b), and {(Ph)2(H)C-P-PtBu2}{μ2-(S-CH2-C6H4-CH2-S)}{tBu2P-P-C(H)(Ph)2} (3c). Next, the reactions of 3a and 3c with metal chlorides led to the growth of desired coordination polymers of copper(I) and silver(I). All the obtained compounds remained stable under atmospheric conditions. [ABSTRACT FROM AUTHOR]

In this work, we report a new type of reactivity of [(BDI*)Ti(Cl){η2-P(SiMe3)-PiPr2}] (1) towards ketones (BDI* = 2,6-diisopropylphenyl-β-methyldiketiminate ligand). In the reaction of 1 with acetone, cyclopentanone or cyclohexanone, a ketone moiety is inserted into Ti–Pphosphanyl or Ti–Pphosphido bonds to form complexes with a new C–P–P moiety, providing [(BDI*)Ti(Cl){η2-P(SiMe3)-PiPr2-C(Me)2O}] (2a), [(BDI*)Ti(Cl){η2-OC(Me)2P(SiMe3)-PiPr2}] (2b), [(BDI*)Ti(Cl){η2-P(SiMe3)-P(iPr)2-{C(CH2)4}O}] (3a), and [(BDI*)Ti(Cl){η2-P(SiMe3)-P(iPr)2-{C(CH2)5}O}] (4a). Starting complex 1 reacts with cyclohexanone, yielding a monocrystalline complex [{(ArN＝C(Me)CHC(Me)＝NAr)C(CH2)5O}Ti(Cl){PiPr2-P(SiMe3)C(CH2)5O}] (4d) with the insertion of two ketone molecules. Interestingly, we found that monoinserted complexes 2a and 3a may be oxidized via a reaction with AgCl, leading to elimination of the –SiMe3 group and oxidation of the titanium atom. This reaction led us to isolate the Ti(IV) complex [(BDI*)Ti(Cl){η2-P-P(iPr)2-{C(CH2)5}O}] (5) in crystalline form. To identify the kinds of products that may be formed and determine which products are the most energetically favoured ones, we conducted a thermodynamic DFT study of 1 towards acetone, cyclopentanone and cyclohexanone. Structures 2a, 2b, 3a, 3e, 4a, 4d, and 5 were characterized by X-ray crystallography, and complex 5 was also identified by NMR spectroscopy. [ABSTRACT FROM AUTHOR]

The first example of CO2 diphosphination is described. Reactions of unsymmetrical diphosphanes with CE2 (E = O, S) catalyzed by BPh3 insert a CE2 molecule into the P–P bond with formation of the products of the general formula R2P–E–C(=E)–PR2. The obtained CO2 adducts arise from synergistic interaction of diphosphane and borane with CO2 molecule. [ABSTRACT FROM AUTHOR]

Herein, the lithium derivative of diphosphane, (Ph)tBuP-P(SiMe3)Li (1), is isolated for the first time and investigated in reactions with β-diketiminate (MeNacnac− = [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6-iPr2C6H3) and PNP-pincer (PNP = N[2-PiPr2-4-methylphenyl]2) Ti(iii) complexes. The β-diketiminate titanium(iii) complex containing the phosphanylphosphido ligand [MeNacNacTi(Cl){η2-P(SiMe3)-P(Ph)tBu}] (2) is prepared via the reaction of [MeNacNacTiCl2·THF] with (Ph)tBuP-P(SiMe3)Li in toluene solution with good yield and purity. The corresponding titanium(iv) complex involving the phosphanylphosphinidene ligand [MeNacNacTi(Cl){η2-P-P(Ph)tBu}] (3) is synthesized via the oxidation of complex (2) with [iBu3PAgCl]4. Interestingly, an analogous PNP titanium(iv) complex, [(PNP)Ti(Cl){η2-P-P(Ph)tBu}] (4), is obtained in the reaction of [(PNP)TiCl2] with (Ph)tBuP-P(SiMe3)Li in toluene solution and a 1 : 1 molar ratio instead of the expected titanium(iii) complex with the phosphanylphosphido ligand. The solid-state structures of (Ph)tBuP-P(SiMe3)Li·3THF (1), [MeNacNacTi(Cl){η2-P(SiMe3)-P(Ph)tBu}] (2), [MeNacNacTi(Cl){η2-P-P(Ph)tBu}] (3) and [(PNP)Ti(Cl){η2-P-P(Ph)tBu}] (4) are determined by single-crystal X-ray diffraction, which reveals that in all obtained complexes, both the phosphanylphosphinidene (Ph)tBuP-P and phosphanylphosphido (Ph)tBuP-P(SiMe3) ligands are bidentate-coordinated to the metal center. [ABSTRACT FROM AUTHOR]