AUROPHILICITY AT SULFUR CENTERS - SYNTHESIS AND REACTIVITY OF THE COMPLEX [S(AU(2)DPPF)] - FORMATION OF POLYNUCLEAR SULFUR-CENTERED COMPLEXES - CRYSTAL-STRUCTURES OF [S(AU(2)DPPF)]CENTER-DOT-2CHCL(3), PPF)[S(AU(2)DPPF)](2)](OTF)(2)CENTER-DOT-8CHCL(3), AND )ME)(2)(AU(2)DPPF)](CLO4)(2)CENTER-DOT-3CH(2)CL(2)

Treatment of [Au2Cl2(mu-dppf)] (dppf = 1,1'-bis(diphenylphosphino)ferr ocene with Li2S (molar ratio 1:1) in ethanol gives a yellow solid [S(A u(2)dppf)] (1). The sulfur atom in complex 1 can coordinate several ne utral or cationic gold(I) fragments giving the trinuclear neutral [S{A u(C6F5)}(Au(2)dppf)] (2) or cationic derivatives [S(AuL)-(Au(2)dppf)]C lO4 [L = CH(2)PPh(3) (3), PPh(3) (4), PPh(2)Me (5)]. A pentanuclear co mplex [Au{S(Au(2)dppf)(2)}]ClO4 (6) is obtained by reaction of 2 equiv of complex 1 with 1 equiv of [Au(tht)(2)]ClO4, in which the central g old atom is bonded to two sulfur atoms. Treatment of compound 1 with [ Au-2(OTf)(2)(mu-dppf)] (OTf = trifluoromethylsulfonate) in a molar rat io 2:1 affords the hexanuclear complex [(mu-Au(2)dppf){S(Au(2)dppf)}(2 )](OTf)(2) (7), in which two SAu3 units are joined through the dppf li gand. The reaction of 1 with 2 equiv of [Au(OClO3)PR(3)] leads to the quadruply bridging derivatives [S(AuPR(3))(2)(Au(2)dppf)](ClO4)(2) [PR (3) = PPh(3) (8), PPh(2)Me (9)]. Crystal structure determinations were performed for complexes, 1, 7, and 9. [S(Au(2)dppf)] (1) crystallizes in the monoclinic space group P-2/n, with a = 12.571(4) Angstrom, b = 10.579(4) Angstrom, c = 15.212(4) Angstrom, beta = 107.84(3)degrees, Z = 2, T = -130 degrees C. [(mu-Au(2)dppf){S(Au(2)dppf)}(2)](OTf)(2) ( 7) is triclinic, P (1) over bar, with a = 15.177(3), b = 18.408(4), c = 27.894(8) Angstrom, alpha = 88.83(2), beta = 84.46(2), gamma = 67.78 (2), Z = 2, T = -100 degrees C. [S(AuPPh(2)Me)(2)(Au(2)dppf)](ClO4)(2) (9) is triclinic, P (1) over bar, with a = 13.727(2) Angstrom, b = 15 .952(3) Angstrom, c = 17.763(2) Angstrom, alpha = 71.738(12)degrees, b eta = 73.264(14)degrees, gamma = 75.96(2)degrees, Z = 2, T = -100 degr ees C. All three complexes display short gold(I)-gold(I) interactions.