Inorganic Chemistry 2001-01-01

Chemistry in Environmentally Benign Media. 7.(1) Chelating Hydroxymethyl-Functionalized Bisphosphines as Building Blocks to Water-Soluble and in-Vitro-Stable Gold(I) Complexes. Synthesis, Characterization, and X-ray Crystal Structures of [Au{(HOH(2)C)(2)PC(6)H(4)P(CH(2)OH)(2)}(2)]Cl and [Au(2){(HOH(2)C)(2)PCH(2)CH(2)P(CH(2)OH)(2)}(2)]Cl(2).

DouglasE. Berning, KatteshV. Katti, CharlesL. Barnes, WynnA. Volkert, AlanR. Ketring

Index: Inorg. Chem. 36 , 2765, (1997)

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Abstract

The reactions of water-soluble bisphosphines (HOH(2)C)(2)PC(6)H(4)P(CH(2)OH)(2) (1) and (HOH(2)C)(2)PCH(2)CH(2)P(CH(2)OH)(2) (2) with NaAuCl(4), in aqueous media, or AuClPPh(3), in biphasic media (aqueous/organic), produced the water/alcoholic-soluble Au(I) complexes [Au{(HOH(2)C)(2)PC(6)H(4)P(CH(2)OH)(2)}(2)]Cl (3), [Au{(HOH(2)C)(2)PCH(2)CH(2)P(CH(2)OH)(2)}(2)]Cl (4), and [Au(2){(HOH(2)C)(2)PCH(2)CH(2)P(CH(2)OH)(2)}(2)]Cl(2) (5) in near quantitative yields. Stability and cysteine-challenge studies of 3 indicate the kinetic inertness of these new complexes. Complex 5 is luminescent in the solid state at room temperature. When excited at 280 nm in non-degassed water at room temperature, the emission spectrum shows a high-energy band at 310 nm and a low-energy band at 560 nm. The large Stokes shift for the low-energy band implies that the emission is phosphorescence. The X-ray structures of 3 and 5, reported in this paper, confirm the gold(I) structures of this new generation of water-soluble transition metal complexes. All compounds were characterized by (31)P and (1)H NMR spectroscopy and mass spectroscopy. X-ray data for 3: monoclinic, P2(1)/m, a = 9.8715(5) _, b = 9.9465(5) _, c = 14.5621(8) _, beta = 106.5930(10) degrees, Z = 2, R = 0.032 (R(w) = 0.050). X-ray data for 5: monoclinic, C2/c, a = 29.7128(14) _, b = 16.7062(8) _, c = 22.3762 (11) _, beta = 117.6970(10) degrees, Z = 16, R = 0.051 (R(w) = 0.072).