An Isolable Mixed P,S‐Bis(ylide) as an Asymmetric Carbon Atom Source

Abstract

Heart of carbon: The first stable asymmetric bis(ylide), N,N′‐(iPr2NCH2CH2NiPr)(Ph)PCSPh2, has been isolated (see picture; C black, N gray). The presence of the two different ligands causes this carbon(0) complex to behave as an asymmetric atomic carbon source.

Synthesis, Structure, and Reactivities of Iminosulfane‐ and Phosphane‐Stabilized Carbones Exhibiting Four‐Electron Donor Ability

“…11 This distance indicates a relatively strong S→C bond in 3 . The P→C bond length of 3 is longer than that in A (1.635 Å), but is similar to that of F (1.667 Å) 11b. 16 The angle at the central carbon increases slightly from salt 3⋅ H (123.6°) to 3 (125.6°).…”

“…In particular, nσ C interacts with σ*(SN) (11.5 kcal mol −1 ), σ*(SC Ph ) (10.8 kcal mol −1 ), and σ*(PC Ar ) (19.3 kcal mol −1 ), whereas nπ C interacts with σ*(SN) (12.9 kcal mol −1 ), σ*(SC Ph ) (28.0 kcal mol −1 ), and σ*(PC Ar ) (25.5 kcal mol −1 ). The total stabilization energy of n–σ*S ( E total =63.2 kcal mol −1 ) is larger than that of n–σ*P ( E total =44.8 kcal mol −1 ), which is in contrast to diamido‐stabilized F (n–σ*S: E total =31.4 kcal mol −1 , n–σ*P: E total =66.0 kcal mol −1 ) 11b. These results suggest that, through the n–σ* interaction, the iminosulfane ligand is more strongly bound to the central carbon atom than the sulfide ligand of PSCs…”

“…Selected bond lengths and angles of 3 and 3⋅ H are listed in Table 1, together with data for A , B , and F and their protonated salts A⋅ H, B⋅ H, and F⋅ H for comparison 1a. 10a, 11b, 16 The P→C (1.663 Å) and S→C (1.602 Å) bond lengths of 3 are significantly shorter than those of the corresponding cationic salt 3⋅ H (P→C: 1.734 Å; S→C: 1.658 Å; Δ P→C =0.071 Å, Δ S→C =0.056 Å). This observation is different from that for F (P→C: 1.667 Å; S→C: 1.684 Å; Δ P→C =0.023 Å, Δ S→C =0.003 Å).…”

Reductive Ring Opening of a Cyclo-Tri(phosphonio)methanide Dication to a Phosphanylcarbodiphosphorane: In Situ UV-Vis Spectroelectrochemistry and Gold Coordination

“…The two lone pairs at the carbon atom of carbodiphosphoranes with σ and π symmetry enable the simultaneous coordination of two metal-based Lewis acids and allow the stabilization of unique electron-deficient main-group-element Lewis acids . Successful isolation of functionalized bisylides was also accomplished by the introduction of imidazolio or sulfonio groups as electron-withdrawing substituents. The implementation of three phosphonio groups into a ylidic carbanion gives tri­(phosphonio)­methanide salts of type C , where the lone pair is strongly delocalized around the CP 3 moiety .…”

Phosphine/Sulfoxide‐Supported Carbon(0) Complex

“…The P1−C1 bond length [1.6563(13) Å] in 2 is significantly shorter than in 1 [1.7190(15) Å] and the value remains slightly longer than those reported for CDPs (1.584–1.648 Å) . The S1−C1 bond length also undergoes significant shortening upon deprotonation [from 1.6539(15) Å in 1 to 1.5929(14) Å in 2 ], this value is the shortest S−C bond length reported to date in the sulfur‐stabilized carbone series (1.602–1.713 Å) ,. The S1−O1, S1−C16, and S1−C22 bond lengths get slightly longer (Δ S−X max=+0.02 Å).…”