Complexes with S-Donor Ligands. 6. Synthesis of the First Family of (Trithiocarbonato)gold Complexes. Crystal Structure of [(PPh3)2N][AuCl2(CS3)]
详细信息 查看全文
- 作者：José ; Vicente ; Marí ; a-Teresa Chicote ; Pablo Gonzá ; lez-Herrero ; and Peter G. Jones
- 刊名：Inorganic Chemistry
- 出版年：1997
- 出版时间：December 3, 1997
- 年：1997
- 卷：36
- 期：25
- 页码：5735 - 5739
- 全文大小：237K
- 年卷期：v.36,no.25(December 3, 1997)
- ISSN：1520-510X
文摘
[(PPh3)2N][Au(SH)2]reacts with CS2 in acetone to give[(PPh3)2N]2[Au2(CS3)2](1) which reacts with iodine(1:1) or PhICl2 (1:1) to give 2 or2', which is an equimolar mixture of the gold(III)complex [(PPh3)2N][Au(CS3)2] (3) and[(PPh3)2N][AuX2] (X = I,Cl). These mixtures decompose in dichloromethane or acetonesolutionsgiving an insoluble dark-red solid analyzing as the mixed-valencecomplex[(PPh3)2N][AuIn{AuIII(CS3)2}n+1](4)with an average n value of 6. The best method toprepare 3 is by reacting 2 with PTo3(To = C6H4Me-4). Thereaction of 4 with[Et2NC(S)S]2 gives[Au(S2CCNEt2)2][Au(CS3)2](5), which can also be obtained by reacting3 with[Au(S2CNEt2)2]ClO4.The complex[(PPh3)2N][AuCl2(CS3)](6) can be obtained by reacting 3 withPhICl2(1:1) or 1 with PhICl2 (1:2). By reactionof 6 with an excess of NaBr, the complex[(PPh3)2N][AuBr2(CS3)](7)can be isolated. Iodine reacts with 3 (1:1) to give[(PPh3)2N][AuI2(CS3)](8). Cationic complexes[Au(CS3)(LL)]CF3SO3 [LL = 1,10-phenanthroline(phen) (9), 2,2'-bipyridyl (bipy) (10)] can beobtained by reacting 6 withTlO3SCF3 and the corresponding bidentateligand (1:2:1). Complex 6 crystallizes in the triclinicsystem, spacegroup P
, with a = 9.482(2) Å,b = 11.888(2) Å, c = 17.303(2) Å,
hars/alpha.gif" BORDER=0> = 108.236(6)
, hars/beta2.gif" BORDER=0 ALIGN="middle"> = 93.340(10), hars/gamma.gif" BORDER=0 >=95.605(10), V = 1835.5 Å3, andZ = 2. The structure was refined to values of R1 =0.0393 [I > 2hars/sigma.gif" BORDER=0 >(I)] andwR2 = 0.0970 (all data). The planar coordination at the goldatom is distorted by the bite of the CS3 ligand[theS(2)-Au-S(1) angle is only 74.49(7)]. TheCSAu bond distances are 1.743(7) and 1.748(7) Å,whereas theCSexo bond is much shorter at 1.608(7)Å.
, with a = 9.482(2) Å,b = 11.888(2) Å, c = 17.303(2) Å,hars/alpha.gif" BORDER=0> = 108.236(6), hars/beta2.gif" BORDER=0 ALIGN="middle"> = 93.340(10), hars/gamma.gif" BORDER=0 >=95.605(10), V = 1835.5 Å3, andZ = 2. The structure was refined to values of R1 =0.0393 [I > 2hars/sigma.gif" BORDER=0 >(I)] andwR2 = 0.0970 (all data). The planar coordination at the goldatom is distorted by the bite of the CS3 ligand[theS(2)-Au-S(1) angle is only 74.49(7)]. TheCSAu bond distances are 1.743(7) and 1.748(7) Å,whereas theCSexo bond is much shorter at 1.608(7)Å.