No abstract

The reaction of 1,2-C 6 H 4 (NHCH 2 PPh 2 ) 2 with chlorosilanes Cl 2 SiHR (R = Ph, Cl) affords the benzosiladiazoles RHSi(NCH 2 PPh 2 ) 2 C 6 H 4 (R = Ph, 1; Cl, 2). The phenyl derivative 1 undergoes chelate-assisted Si−H activation with [RuPhCl(CO)(PPh 3 ) 2 ] and [RhCl(PPh 3 ) 3 ] to afford the structurally characterized silyl pincer complexes [RuCl(CO)-(PPh 3 ){κ 3 -P,Si,P′-SiPh(NCH 2 PPh 2 ) 2 C 6 H 4 }] (3) and [RhHCl-(PPh 3 ){κ 3 -P,Si,P′-SiPh(NCH 2 PPh 2 ) 2 C 6 H 4 }] (4). The reaction of 4 with [Et 2 NH 2 ][S 2 CNEt 2 ] affords the complex [RhH-(S 2 CNEt 2 ){κ 3 -P,Si,P′-SiPh(NCH 2 PPh 2 ) 2 C 6 H 4 }] (5), structural data for which demonstrate a pronounced trans influence for the σ-silyl donor.

The reaction of As(NMe2)3 with Mes*PHLi provides a direct source of the 1,3-diphosphaarsa-2-allyl anion, [(Mes*P)2As](-) (isoelectronic with the allyl anion). The equilibrium between the E,E and E,Z isomers of this anion depends on the extent of Li(+) ion-pairing.

Rapid testing of hydrophilic and hydrophobic basic immobilized amine sorbents (BIAS) for CO2 capture stability under practical conditions was achieved by direct contact of the sorbents with flowing liquid water. Losses in both CO2 capture capacity and amine content of sorbents after exposure to 0.5 mL min−1 of H2O at 25 °C for 40 min followed similar trends as losses observed after exposure to N2/steam (105 °C, 7 % H2O) for 10 h. We also found that hydrophobic TMPED helped stabilize sorbents to H2O, which was confirmed by DRIFTS and combined TGA‐DSC.

The synthesis of a range of 1,2-diphospholides can be achieved by a one-pot procedure involving the reactions of aromatic primary phosphines bearing ortho-CH 2 substituents with the superbase mixture of n BuLi/Sb(NMe 2 ) 3 in the presence of the Lewis base donor TMEDA (Me 2 NCH 2 CH 2 NMe 2 ). The synthesis of the parent benzo-1,2-diphospholide and the substituted derivatives 4-methoxybenzo-1,2-diphospholide, 9-methylbenzo-1,2-diphospholide, and naphtho-1,2-diphospholide are reported from readily prepared primary phosphines. Bulk synthesis of the potassium salt of the previously reported 4,6dimethylbenzo-1,2-diphospholide anion using this route provides a convenient starting material for reactivity studies.