Synthesis and characterization of dioxorhenium complexes derived from water-soluble diphosphine tetraphosphonates

Different co-ordination modes of the new, water-soluble, triphosphine PhP[CH2CH2P(CH2OH)2]2 with PtII, PdII, RhI and ReV

“…Compounds I-III were characterized by 1 H, 13 C and 31 P NMR spectroscopy. Fast atom bombardment mass spectrometry was used to identify the molecular ion for the new (hydroxyalkyl)triphosphine III.…”

“…When dissolved in water, it reacted readily with [Pt(cod)]Cl 2 (cod = cycloocta-1,5-diene), [Pd(PhCN) 2 ]Cl 2 , [{RhCl(cod)} 2 ] and [ReO 2 I(PPh 3 ) 2 ], each in CH 2 Cl 2 , to provide complexes 1-4 of Pt II , Pd II , Rh I and Re V respectively. All of the new compounds were characterized by 1 H, 13 C and 31 P NMR spectroscopies. Compound 1 was further characterized by 195 Pt NMR spectroscopy.…”

“…13 C NMR (D 2 O): δ 11.0 (dd, 1 J PC = 14.5, 2 J PC = 5.18, PCH 2 CH 2 -PC 6 H 5 ), 14.1 (dd, 1 J PC = 44.7, 2 J PC = 19.1, PCH 2 CH 2 PC 6 H 5 ), 57.3 (d, 1 J PC = 10.6, PCH 2 OH), 114.3 (d, 1 J PC = 77.7, PC 6 H 5 ), 129.5 (d, 2 J PC = 64.9, o-C of C 6 H 5 ), 132.1 (d, 3 J PC = 8.3 Hz, m-C of C 6 H 5 ) and 135.0 (s, p-C of C 6 H 5 ). 31 P NMR (D 2 O): δ 29.9 (t, 3 J PP = 37.7, PC 6 H 5 ) and Ϫ20.1 (d, 3 J PP = 37.7 Hz, PCH 2 OH).…”

“…Aqueous formaldehyde (61 mmol) was placed in oxygen-free ethanol (50 cm 3 ) and purged with nitrogen gas for 2 h at 25 ЊC. Compound II(13 mmol) was added dropwise with stirring at 25 ЊC. The reaction was complete in 2 h, as monitored by 31 P NMR spectroscopy.…”

Syntheses and Characterization of Chemically Flexible, Water-Soluble Dithio−Bis(phosphine) Compounds: (HOH2C)2P(CH2)2S(CH2)3S(CH2)2P(CH2OH)2, (HOH2C)2PCH2CH2S(CH2)4SCH2CH2P(CH2OH)2, and (HOH2C)2PCH2CH2CH2S(CH2)3SC

“…Our recent studies have demonstrated that a new class of chelating bis(phosphine)s of the type ((HOH 2 C) 2 PCH 2 CH 2 P(CH 2 OH) 2 (bis((hydroxymethyl)phosphino)ethane, HMPE) and (HOH 2 C) 2 PC 6 H 4 P(CH 2 OH) 2 (bis((hydroxymethyl)phosphino)benzene, HMPB) are oxidatively stable in air and also in aqueous solutions. , These properties coupled with the high in vitro / in vivo stability of Tc-99m complexes derived from HMPE and HMPB presented prospects for further modification of (hydroxymethyl)phosphine-based ligands . As part of our ongoing studies in the design and development of functionalized phosphines − for use in nuclear medicine, we report herein (a) the synthesis of a new series of water-soluble ligands based on dithio−bis(phosphine) backbones, 1,3-bis((bis((hydroxymethyl)phosphino)ethyl)thio)propane, (HOH 2 C) 2 P(CH 2 ) 2 S(CH 2 ) 3 S(CH 2 ) 2 P(CH 2 OH) 2 ( 1 ), 1,4-bis((bis((hydroxymethyl)phosphino)ethyl)thio)butane, (HOH 2 C) 2 PCH 2 CH 2 S(CH 2 ) 4 SCH 2 CH 2 P(CH 2 OH) 2 ( 4 ), and 1,3-bis((bis((hydroxymethyl)phosphino)propyl)thio)propane, (HOH 2 C) 2 PCH 2 CH 2 CH 2 S(CH 2 ) 3 SCH 2 CH 2 CH 2 P(CH 2 OH) 2 ] ( 7 ), (b) their coordination chemistry with Re(V), demonstrating the importance of ligand chain size in producing complexes with 1:1 metal to ligand ratios, and (c) X-ray crystal structures of [ReO 2 (HOH 2 C) 2 P(CH 2 ) 2 S(CH 2 ) 3 S(CH 2 ) 2 P(CH 2 OH) 2 ] 2 (Cl) 2 ( 8 ), [ReO 2 (HOH 2 C) 2 P(CH 2 ) 2 S(CH 2 ) 4 S(CH 2 ) 2 P(CH 2 OH) 2 ] 2 (ReO 4 - ) 2 ( 9 ), and [ReO 2 (HOH 2 C) 2 P(CH 2 ) 3 S(CH 2 ) 3 S(CH 2 ) 3 P(CH 2 OH) 2 ](Cl) ( 10 ). In vitro studies demonstrating the kinetic inertness of new water-soluble Re(V) complexes derived from dithio−bis(phosphine) ligands are also described.…”