Synthesis and characterization of complexes of the {ReO} core with SNS and S donor ligands.

The reaction of [ReOCl(3)(PPh(3))(2)] with N,N-bis(2-mercaptoethyl)benzylamine and 4-bromobenzenethiol allowed for the isolation of [ReO{eta(3)-(SCH(2)CH(2))(2)N(CH(2)C(6)H(5))}-(eta(1)-C(6)H(4)Br-4-S)] (1). The reaction of [ReOCl(3)(PPh(3))(2)] with [(HSCH(2)CH(2))(2)N(CH(2)C(5)H(4)N)] and the appropriate thiol in chloroform treated with triethylamine has led to the isolation of a series of neutral rhenium complexes of the type [ReO{eta(3)-(SCH(2)CH(2))(2)N(CH(2)C(5)H(4)N)}(eta(1)-C(6)H(4)X-4-S)] (X = Br (2), Cl (3), F (4), and OCH(3) (5)) and [ReO{eta(3)-(SCH(2)CH(2))(2)N(CH(2)C(5)H(4)N)}(eta(1)-C(6)H(4)OCH(3)-4-CH(2)S)] (6). Likewise, under similar reaction conditions, the use of the related tridentate ligand, [(HSCH(2)CH(2))(2)N(CH(2)CH(2)C(5)H(4)N)], has led to the isolation of a series of rhenium complexes of the type [ReO{eta(3)-(SCH(2)CH(2))(2)N(CH(2)CH(2)C(5)H(4)N)}(eta(1)-C(6)H(4)X-4-S)] (X=Br (7), Cl (8), OCH(3) (9)), as well as [ReO{eta(3)-(SCH(2)CH(2))(2)N(CH(2)CH(2)C(5)H(4)N)}(eta(1)-C(6)H(4)Cl-4-CH(2)S)].0.5CH(3)(CH(2))(4)CH(3) (10). These compounds are extensions of the '3+1' approach to the synthesis of materials with the {MO}(3+) core (M=Tc and Re), which have applications in nuclear medicine. The ligands chosen allow systematic exploration of the consequences of para-substitution on the monodentate thiolate ligand [S] and of derivatization of the substituent R on the tridentate aminodithiol ligand [SNS] of the type (HSCH(2)CH(2))(2)NR. Such modifications can influence lipophilicity, charge, size and molecular weight of the complex and consequently the biodistribution.