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Synthesis of complexes of Re V , Ru II , Os II , Rh I , Ir I and Ir III . Crystal and molecular structures of [ReO(OH)(SC6H4 SiPh3-2)2(PPh3)], [ReH4(SC6H4SiPh3-2)(PPh3)3] and [IrH(SC6H4SiPh3-2)2(PMePh2)3]

1995; Royal Society of Chemistry; Issue: 19 Linguagem: Inglês

10.1039/dt9950003143

2050-5671

Mustafa T. Ahmet, Can‐Zhong Lu, Jonathan R. Dilworth, John R. Miller, Yifan Zheng, David E. Hibbs, Michael B. Hursthouse, K. M. Abdul Malik,

Metal complexes synthesis and properties

The rhenium(V) precursors [ReOX3(PPh3)2](X = Cl or Br) reacted with 2-triphenylsilylbenzenethiol in methanol in the presence of base to give [ReO(Cl)(SC6H4SiPh3-2)2(PPh3)]1 and [ReO(OH)(SC6H4SiPh3-2)2(PPh3)]2 respectively. In the presence of NaBH4 and no base the blue thiolate polyhydride [ReH4(SC6H4SiPh3-2)(PPh3)3]3 was formed in high yield. The crystal structures of 2 and 3 were determined and showed 2 to be monomeric with distorted trigonal-bipyramidal geometry and the oxide and hydroxide ligands in equatorial sites. The thiolate and phosphine ligands of 3 are in a tetrahedral array with the hydride ligands assumed to be in capping sites on the tetrahedral faces. Reaction of the thiol with [IrCl3(PMePh2)3] in methanol in the presence of NEt3 gave [IrH(SC6H4SiPh3-2)2(PMePh2)3]4 in good yield. Its crystal structure revealed the geometry about the Ir to be pseudo-octahedral with mer phosphine ligands and cis thiolates, and the hydride presumed to be in a vacant site trans to a thiolate ligand. The complex [IrCl(CO)(PPh3)2] reacted under similar conditions to give monomeric [Ir(SC6H4SiPh3-2)(CO)(PPh3)2]6 whereas [RhCl(CO)(PPh3)2] gave [Rh2(µ-SC6H4SiPh3-2)2(CO)2(PPh3)2]5; [OsH(Cl)(PPh3)3] gave [OsH(SC6H4SiPh3-2)(CO)(PPh3)3]7 whereas [RuH(Cl)(PPh3)2] formed [Ru(SC6H4SiPh3-2)(CO)(PPh3)2]8. The potentially bidentate thiol SiPh2(C6H4SH-2)2 gave a series of products with the same precursors which proved difficult to characterise unequivocally in the absence of X-ray structural data. The geometry adopted by the SC6H4SiPh3-2 ligand was analysed in some detail and contrasted with symmetrically 2,6-disubstituted aromatic thiolates.