Reactions of a Phosphinoimino-thiazoline-Based Metalloligand with Organic and Inorganic Electrophiles and Metal-Induced Ligand Rearrangements

The reaction of the neutral Pt(II) bischelated complex cis -[ Pt{Ph 2 PN ··· C ··· NCH 2 CH 2 S } 2 ] ([Pt( 2 −H ) 2 ], 1; 2 = Ph 2 PNH C═NCH 2 CH 2 S, N -(diphenylphosphino)-thiazoline-2-amine) with the organic electrophile EtN═C═S yielded complex [Pt( 2 −H )( 2 −H ·EtNCS)] ( 3 ) as a result of the nucleophilic attack of the coordinated 2-((diphenylphosphino)imino)thiazolidin-3-yl moiety on the heteroallene carbon atom and coordination of the sulfur atom to the metal. The reaction of 1 with [Cu(NCMe) 4 ]PF 6 also proceeded by nucleophilic attack of the P−N nitrogen atom on Cu(I) and afforded the coordination polymer [ 1 ·Cu] ∞ [PF 6 ] ∞ ( 4 ). The reaction of ligand 2 with NiBr 2 · x H 2 O resulted in a molecular rearrangement and afforded an unexpected pentacoordinated diamagnetic complex, [Ni( 2 ){ trans -Ph 2 PN═ C−N(PPh 2 )CH 2 CH 2 S}Br]Br ( 6 ), which likely arises from a metal-templated ligand coupling in the presence of water acting as promoter. Complex 6 was evaluated as a precatalyst for ethylene oligomerization, showing good activities with EADC as cocatalyst. All new complexes were structurally characterized by X-ray diffraction.