1233197-75-5Relevant academic research and scientific papers
Synthesis, characterization and structures of cyclic organorhodium complexes of the type [Rh{CH(SO2Ph)CH2CH 2YR2-κC,κY}L2] (YR2 = PPh2, NMe2; L2 = diphosphine, cyclooctadiene)
Block, Michael,Wagner, Christoph,Gomez-Ruiz, Santiago,Steinborn, Dirk
, p. 4636 - 4646 (2010/08/21)
Reactions of dinuclear chloridorhodium(i) complexes [(RhL2) 2(μ-Cl)2] (L2 = PP: Me2P(CH 2)2PMe2, dmpe, 7a; Ph2PCH 2PPh2, dppm, 7b; Ph2P(CH2) 2PPh2, dppe, 7c; Ph2P(CH2) 3PPh2, dppp, 7d; L2 = cycloocta-1,5-diene, cod, 5) with lithiated γ-phosphino- and γ-aminofunctionalized propyl phenyl sulfones (Li[CH(SO2Ph)CH2CH2PPh 2], 2; Li[CH(SO2Ph)CH2CH2NMe 2], 4) led to the formation of organorhodium inner complexes of the type [Rh{CH(SO2Ph)CH2CH2PPh2- κC,κP}(PP)] (8a-d), [Rh{CH(SO2Ph)CH2CH 2NMe2-κC,κN}(PP)] (9a-d), [Rh{CH(SO 2Ph)CH2CH2PPh2-κC,κP} (cod)]·LiCl (11·LiCl) and [Rh{CH(SO2Ph)CH 2CH2NMe2-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 [(RhL2) 2(μ-Cl)2] (L2 = PP, 7a-d; cod, 5; (C 2H4)2, 6) with the (non-lithiated) γ-phosphinofunctionalized propyl phenyl sulfone PhSO2CH 2CH2CH2PPh2 (1) resulting in the formation of complexes having the sulfone κP coordinated ([RhClL 2(Ph2PCH2CH2CH2SO 2Ph-κP)] (L2 = PP, 10a-d; cod, 13; (C 2H4)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, 13C, 31P).
