On the Reactivity of Rhodium(I) Complexes with κP-Coordinated γ-Phosphino-Functionalized Propyl Phenyl Sulfide Ligands: Routes to Cyclic Rhodium Complexes with κC,κP- and κP,κS-Coordinated Ligands as Well as Bis(diphenylphosphino)methanide Ligands

Abstract

Reactions of dinuclear μ-chlorido rhodium(I) complexes [(RhL2)2(μ-Cl)2] (L2 = cycloocta-1,5-diene, cod, 3; L2 = P∧P: Ph2PCH2PPh2, dppm, 4a; Ph2P(CH2)2PPh2, dppe, 4b; Ph2P(CH2)3PPh2, dppp, 4c; Me2P(CH2)2PMe2, dmpe, 4d) with γ-phosphino-functionalized propyl phenyl sulfides PhSCH2CH2CH2PR2 (R = Ph, 1; Cy, 2) afforded mononuclear rhodium(I) complexes of the type [RhCl(R2PCH2CH2CH2SPh-κP)L2] ] (R = Ph/L2 = P∧P, 5a−c; R = Ph/L2 = cod, 6; R = Cy/L2 = P∧P, 7a−d; R = Cy/L2 = cod, 8). Single-crystal X-ray diffraction analysis of 7b·C6H6 exhibited the expected square-planar coordination of the rhodium atom having coordinated dppe-κ2P,P′, Cy2PCH2CH2CH2SPh-κP, and a chlorido ligand. Deprotonation of complexes 5b/c, 6, 7b/c, and 8 with lithium diisopropyl amide (LDA) yielded, with a selective deprotonation of the CH2 group next to the sulfur atom (α-CH2 group), complexes of the type [Rh{CH(SPh)CH2CH2PR2-κC,κP}L2] (13b/c, 14, 15b/c, 16), thus being organorhodium intramolecular coordination compounds. Unexpectedly, reac...