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The neutral metal complexes cis-[Pt(CH3)2{o-Ph2PN(H)C6H4C(O)CH3-P}2] and [RhCl2(Cp*){o-Ph2PN(H)C6H4C(O)Ph-P}] are excellent precursors for new five-membered M−P−N−C−C metallacycles via σ(Csp 2 −H) bond activation. The synthesis and characterization including the molecular structures of cis-[Pt{o-Ph2PN(H)C6H3C(O)CH3-P,C}2]·OEt2 and [RhCl(Cp*){o-Ph2PN(H)C6H3C(O)Ph-P,C}]·0.5CHCl3 are reported.

a b s t r a c tThe synthesis of three new ester functionalised bis(phosphino)amines Ph 2 PN{R}PPh 2 [R ¼ C 6 H 4 (3-CO 2 Me) 1a; C 6 H 3 (3,5-CO 2 Me) 2 1b; C 6 H 4 (4-CO 2 Me) 1c] upon stoichiometric reaction of Ph 2 PCl and the appropriate H 2 N{R} in Et 2 O is described. Reaction of 1 equiv. of 1aÀc with MCl 2 (cod) (M ¼ Pt, Pd) in CH 2 Cl 2 afforded the dichlorometal(II) complexes PtCl 2 (1a) 2a, PtCl 2 (1b) 2b, PtCl 2 (1c) 2c and PdCl 2 (1b) 2`b respectively. The corresponding dibromo (and diiodo) platinum(II) complexes 3b (and 4b) were synthesised, in >80% isolated yields, from PtBr 2 (cod) or PtI 2 (cod). When a suspension of 2b in MeOH was stirred at r.t. for ca. 16 h the mixed complex cis-PtCl 2 [Ph 2 PNH{R}](Ph 2 POMe) 5a [R ¼ C 6 H 3 (3,5-CO 2 Me) 2 ] was cleanly generated. Metathesis of 5a using excess NaBr or NaI in MeOH/acetone afforded cisPtBr 2 [Ph 2 PNH{R}](Ph 2 POMe) 5b or cis-PtI 2 [Ph 2 PNH{R}](Ph 2 POMe) 5c. Methanolysis of PtCl 2 (1a) 2a at ambient temperature afforded, in low yield (18%), the regiospecific P,C-orthometallated complex cis-PtCl [Ph 2 PNH{C 6 H 3 (3-CO 2 Me)}](Ph 2 POMe) 6. We speculate the CÀH activated complex 6 is obtained via initial formation of cis-PtCl 2 [Ph 2 PNH{C 6 H 4 (3-CO 2 Me)}](Ph 2 POMe) 7. A similar observation was also found using 2c whereupon examination of the isolated solid, by 31 P{ 1 H} NMR spectroscopy, revealed formation of three complexes namely orthometallated cis-PtCl[Ph 2 PNH{C 6 H 3 (4-CO 2 Me)}](Ph 2 POMe) 9, cis-PtCl[Ph 2 PNH{C 6 H 4 (4-CO 2 Me)}](Ph 2 POMe) 10 and cis-PtCl 2 (Ph 2 POMe) 2 8. All new compounds reported here have been characterised by multinuclear NMR and IR spectroscopy, microanalysis and in six cases by single crystal X-ray crystallography. The X-ray structure of cis-PtCl[Ph 2 PNH{C 6 H 3 (3-CO 2 Me)}](Ph 2 POMe) 6 revealed selective CÀH cycloplatination at the 6-position (as opposed to the 2-position) of the N-arene ring.

Aminobenzothiazole-functionalised phosphane 1 and its corresponding phosphorus(V) analogues 2-4 were synthesised in high yields. New 1D polymeric salts K[ClC 6 H 3 NC(S)NP-(E)Ph 2 ] ϱ (E = O 5; E = S 6) were shown, by using singlecrystal X-ray diffraction, to exhibit unique potassium metal ion coordination through either κ 3 -N 2 O tridentate (E = O) or κ 2 -N 2 bridging (E = S) modes. In contrast, κ 2 -NE chelation (E = S, Se) was observed upon complexation to a range of metal