Synthesis, characterization and structures of cyclic organorhodium complexes of the type [Rh{CH(SO_2Ph)CH_2CH _2YR_2-κC,κY}L_2] (YR_2 = PPh_2, NMe_2; L_2 = diphosphine, cyclooctadiene)

摘要

Reactions of dinuclear chloridorhodium(i) complexes [(RhL_2) _2(μ-Cl)_2] (L_2 = PP: Me_2P(CH _2)_2PMe_2, dmpe, 7a; Ph_2PCH _2PPh_2, dppm, 7b; Ph_2P(CH_2) _2PPh_2, dppe, 7c; Ph_2P(CH_2) _3PPh_2, dppp, 7d; L_2 = cycloocta-1,5-diene, cod, 5) with lithiated γ-phosphino- and γ-aminofunctionalized propyl phenyl sulfones (Li[CH(SO_2Ph)CH_2CH_2PPh _2], 2; Li[CH(SO_2Ph)CH_2CH_2NMe _2], 4) led to the formation of organorhodium inner complexes of the type [Rh{CH(SO_2Ph)CH_2CH_2PPh_2- κC,κP}(PP)] (8a-d), [Rh{CH(SO_2Ph)CH_2CH _2NMe_2-κC,κN}(PP)] (9a-d), [Rh{CH(SO _2Ph)CH_2CH_2PPh_2-κC,κP} (cod)]·LiCl (11·LiCl) and [Rh{CH(SO_2Ph)CH _2CH_2NMe_2-κC,κN}(cod)]·LiCl (12·LiCl), respectively. Single-crystal X-ray diffraction analysis of 9c·THF, 11 and 12 exhibited in all three compounds a distorted square planar coordination of the rhodium atoms having bidentately coordinated neutral co-ligands (cod, 11, 12; dppe, 9c) and anionic α-phenylsulfonyl γ-phosphinopropyl (κC,κP; 11) and γ-aminopropyl ligands (κC,κN; 12, 9c), thus being typical organorhodium inner complexes. Furthermore, organorhodium inner complexes of type 8 were obtained in reactions of the dinuclear chloridobridged rhodium complexes [(RhL_2) _2(μ-Cl)_2] (L_2 = PP, 7a-d; cod, 5; (C _2H_4)_2, 6) with the (non-lithiated) γ-phosphinofunctionalized propyl phenyl sulfone PhSO_2CH _2CH_2CH_2PPh_2 (1) resulting in the formation of complexes having the sulfone κP coordinated ([RhClL _2(Ph_2PCH_2CH_2CH_2SO _2Ph-κP)] (L_2 = PP, 10a-d; cod, 13; (C _2H_4)_2, 14) which were deprotonated (10a-d, 13) at the α-C atom with lithium diisopropyl amide (LDA) in a subsequent reaction. Single-crystal X-ray diffraction analysis of 10c (PP = dppe) revealed the expected square-planar coordination geometry of Rh. The identities of all rhodium complexes have been unambiguously proved by microanalyses and NMR spectroscopy (~1H, ~(13)C, ~(31)P).