N,O‐Chelates of Group 4 Metals: Contrasting the Use of Amidates and Ureates in the Synthesis of Metal Dichlorides

A series of dichloride complexes of titanium and zirconium with amidate and ureate ancillary ligands have been prepared. Three examples of bis(amidate)dichlorotitanium and zirconium complexes were effectively synthesized through salt metathesis with metal tetrachloride as starting materials. Optimum results were achieved using sodium amidate salts formed from sodium bis(trimethylsilyl)amide and neutral amide proligands, while other methods were ineffective. Use of electron‐donating ureate ligands in lieu of amidates enables preparation through alternate routes. Protonolysis of Ti(NMe2)2Cl2 and Zr(NMe2)2Cl2(dme) with urea proligands leads to dichlorobis(ureate) complexes in good yield. Using a tethered bis(ureate) ligand eliminates the fluxional behaviour and coordination isomerism observed for both bis(amidate) and bis(ureate) zirconium complexes.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)