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• 1233197-58-4 3-(diphenylphosphino)propyl phenyl sulfone 
• 4111-54-0 lithium diisopropyl amide 

Relevant academic research and scientific papers

Rhodium(I) complexes with κp coordinated ω- phosphinofunctionalized alkyl phenyl sulfide, sulfoxide and sulfone ligands and their reactions with sodium bis(trimethylsilyl)amide and Ag[BF4]

Reactions of ω-diphenylphosphinofunctionalized alkyl phenyl sulfides Ph2P(CH2)nSPh (n = 1, 1a; 2, 2a; 3, 3a), sulfoxides Ph2P(CH2)nS(O)Ph (n = 1, 1b; 2, 2b; 3, 3b) and sulfones Ph2P(CH2)nS(O) 2Ph (n = 1, 1c; 2, 2c; 3, 3c) with dinuclear chlorido bridged rhodium(I) complexes [(RhL2)2(μ-Cl)2] (L2 = cycloocta-1.5-diene, cod, 4; bis(diphenylphosphino)ethane, dppe, 5) afforded mononuclear Rh(I) complexes of the type [RhCl{Ph 2P(CH2)nS(O)xPh-κP}(cod)] 1 (n/x = 1/0, 6a; 1/1, 6b; 1/2, 6c; 2/0, 8a; 2/1, 8b; 2/2, 8c; 3/0, 10a; 3/1, 10b; 3/2, 10c) and [RhCl{Ph2P(CH2) nS(O)xPh-κP}(dppe)] (n/x = 1/0, 7a; 1/1, 7b; 1/2, 7c; 2/0, 9a; 2/1, 9b; 2/2, 9c; 3/0, 11a; 3/1, 11b; 3/2, 11c) having the P^S(O)x ligands κP coordinated. Addition of Ag[BF4] to complexes 6-11 in CH2Cl2 led with precipitation of AgCl to cationic rhodium complexes of the type [Rh{Ph2P(CH 2)nS(O)xPh-κP,κS/O}L 2][BF4] having bound the P^S(O)x ligands bidentately in a κP,κS (13a-18a, 15b-18b) or a κP,κO (13b, 14b, 13c-18c) coordination mode. Unexpectedly, the addition of Ag[BF 4] to 6a in THF afforded the trinuclear cationic rhodium(I) complex [Rh3(μ-Cl)(μ-Ph2PCH2SPh-κP: κS)4][BF4]2·4THF (12·4THF) with a four-membered Rh3Cl ring as basic framework. Addition of sodium bis(trimethylsilyl)amide to complexes 6-11 led to a selective deprotonation of the carbon atom neighbored to the S(O)x group (α-C) yielding three different types of organorhodium complexes: a) Organorhodium intramolecular coordination compounds of the type [Rh{CH{S(O) xPh}CH2CH2PPh2-κC,κP} L2] (22a-c, 23a-c), b) zwitterionic complexes [Rh{Ph 2PCHS(O)xPh-κP,κS/O}L2] having κP,κS (21a, 21b) and κP,κO (20b/c, 21c) coordinated anionic [Ph2PCHS(O)xPh] ligands, and c) the dinuclear rhodium(I) complex [{Rh{μ-CH(SPh)PPh2-κC:κP}(cod)} 2] (19). All complexes were fully characterized spectroscopically and complexes 15b, 15c, 12·4THF and 19·THF additionally by X-ray diffraction analysis. DFT calculations of zwitterionic complexes gave insight into the coordination mode of the [Ph2PCHS(O)Ph] ligand (κP,κS versus κP,κO).

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)

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).