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).
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) Å, b = 9.9465(5) Å, c = 14.5621(8) Å, 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) Å, b = 16.7062(8) Å, c = 22.3762 (11) Å, beta = 117.6970(10) degrees, Z = 16, R = 0.051 (R(w) = 0.072).
Berning
Douglas E.
DE
Center for Radiological Research and Missouri University Research Reactor, Department of Chemistry, University of Missouri, H. S. Truman Memorial V. A. Hospital, Columbia, Missouri 65203.
Katti
Kattesh V.
KV
Barnes
Charles L.
CL
Volkert
Wynn A.
WA
Ketring
Alan R.
AR