Diverse Coordination Behaviour of Phosphorus(V)‐Functionalised 6‐Chloroaminobenzothiazole Anions at Various Metal Centres

Aminobenzothiazole-functionalised phosphane 1 and its corresponding phosphorus(V) analogues 2-4 were synthesised in high yields. New 1D polymeric salts K[ClC6H3NC(S)NP(E)Ph-2](infinity) (E = O 5; E = S 6) were shown, by using single-crystal X-ray diffraction, to exhibit unique potassium metal ion coordination through either kappa(3)-N2O tridentate (E = O) or kappa(2)-N-2 bridging (E = S) modes. In contrast,kappa(2)-NE chelation (E = S, Se) was observed upon complexation to a range of metal fragments including {Ir(eta(5)-Cp*)Cl} (E = S 8; E = Se 9), {Rh(eta Cp-5*)Cl} (E = S 10; E = Se 11), {Ru(eta(6)-p-MeC(6)H(4)iPr)Cl} (E = S 12), {Ru(eta(6)-C6Me6)Cl} (E = S 13) and {Pt(PMe2Ph)Cl} (E = S 14). All new compounds were characterised by a combination of multinuclear NMR, FTIR and microanalysis. Seven compounds were structurally characterised by using single-crystal X-ray crystallography.