The chemistry of heteroallyl derivatives of technetium. Reactivity of [TcNCl2(PPh3)2] and [Tc(CO) 3Cl(PPh3)] with thiazetidine ligands, crystal structures of [Tc(CO)2(PPh3)2{PhN=C(OEt)S}] and [TcN(Cl)(PPh3)-{PhN=C(OEt)S}]

The complex [Tc(CO)3Cl(PPh3)] reacts with the sodium salt of PhNC(OEt)SH to give the thiazetidine complex [Tc(CO) 2(PPh3)2{PhN=C(OEt)S}] (1). The complex [TcNCl2(PPh3)2] reacts with an excess of the neutral ligand to give [TcN(Cl)(PPh3){PhN=C(OEt)S}] (2). When the reaction is carried out in presence of the ligand salt the disubstituted complex [TcN{PhN=C(OEt)S}2] (3) is obtained. The crystal structures of (1) and (2) were determined by X-ray crystallography and refined to conventional R factors of 0.0295 and 0.0649 respectively. Compound (1) is monoclinic, space group P21, with a = 12.825(5), b = 16.713(5), c = 9.480(5) Å, β = 94.29(3)°, and Z = 2. The technetium environment is distorted octahedral. Selected bond distances are: Tc-P(1) 2.423(1) Å, Tc-P(2) 2.456(1), Tc-S 2.529(1), Tc-N 2.228(5), and Tc-C 1.89(1) Å (mean). Compound (2) is triclinic, space group P1, with a = 9.428(5), b = 10.237(5), c = 15.603(5) Å, α = 89.29(3), β = 102.74(3), γ = 115.61 (3)°, and Z = 2. The environment ...