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Dithiolates as bridging ligands in di- and trinuclear gold complexes. X-ray structures of [Au2(3,4-S2C6H3CH 3)(PPh3)2], [Au2(1,3-S2C6H4)(PPh 3)2], [Au3(3,4-S2C6H ...
Concepción Gimeno,Jones, Peter G.,Laguna, Antonio,Laguna, Mariano,Terroba, Raquel
, p. 3932 - 3938 (2008/10/08)
Full title: Dithiolates as bridging ligands in di- and trinuclear gold complexes. X-ray structures of [Au2(3,4-S2C6H3CH 3)(PPh3)2], [Au2(1,3-S2C6H4)(PPh 3)2], [Au3(3,4-S2C6H3CH 3)(PPh3)3]ClO4, and [Au(PPh2Me)2][Au(3,4-S2C6H 3CH3)2]. The reaction of [AuCl(AsPh3)] with potassium 1,2-benzenedithiolate or 3,4-toluenedithiolate (2:1 ratio) leads to [Au2(S-S)(AsPh3)]n [S-S = 1,2-S2C6H4 (1), 3,4-S2C6H3CH3 (2)] but with 1,3-benzenedithiolate the homoleptic [Au2(1,3-S2C6H4)]n (3) is obtained. Other dinuclear complexes have been prepared by reacting 1-3 with phosphines, namely [Au2(S-S)(PR3)2] [S-S = 1,2-S2C6H4 (4, 5), 3,4-S2C6H3CH3 (6, 7), 1,3-S2C6H4(8, 9); PR3 = PPh3, PPh2-Me]. The reaction of [Au2(S-S)(PPh3]2] (4 and 6) with equimolecular amounts of [Au(PPh3)(acetone)]ClO4 affords the trinuclear complexes [Au3(S-S)(PPh3)3]ClO4 [S-S = 1,2-S2C6H4 (10) and 3,4-S2C6H3CH3 (11)]. Gold-(I)/gold(III) complexes [Au(PR3)2][Au(3,4-S2C6H 3CH3)2] [PR3 = PPh3 (12), PPh2Me (13)] have been obtained as byproducts in the preparation of 6 and 7. X ray structure determinations were performed for complexes 6, 8, 11 and 13. Complex 6 crystallizes in the space group P21, monoclinic, with a = 10.771(4) ?, b = 10.726(3) ?, c = 16.752(6) ?, β = 101.02(3)°, and Z = 2. Compound 8 crystallizes in space group Fdd2, orthorhombic, with a - 31.182(8) ?, b = 46.537(12) ?, c = 8.782(3) ?, and Z = 16. Complex 11 crystallizes in space group C2/c, monoclinic, with a = 39.583(8) ?, b = 11.347(3) ?, c = 31.703(7) ?, β = 120.66(2)°, and Z = 8. Compound 13 crystallizes in space group C2/c, monoclinic, with a = 17.890(7) ?, b = 11.038(6) ?, c = 20.817(11) ?, β = 110.96(3)°, and Z = 4. Short Au?Au contacts (ca. 3 ?) are observed in 6 and 11 (intramolecular) and 8 (intermolecular). Complexes 6 and 11 also display intramolecular Au-S contacts of ca. 2.6-2.7 ?, leading to an increase of coordination number (to 3) at Au(1) in 6 and Au(2) in 11.
