Neutral and anionic transition metal complexes supported by decafluorodiphenylamido ligands: X-ray crystal structures of {Na(THF)2} {Ti[N(C6F5)2]4}, {K(η6-C6H5Me)2} {ZrCl2[N(C6F5)2]3}, K{VCl[N(C6F5)2]3}, Fe[N(C6F5)2]2(THF)2 and Co[N(C6F5)2]2(py)2

Abstract Reaction of MN(C 6 F 5 ) 2 (M=Na, K) with transition metal halides results in the formation of transition metal complexes incorporating decafluorodiphenylamido ligands. TiCl 3 (THF) 3 reacts with 3 equiv. NaN(C 6 F 5 ) 2 to yield the ‘metallate’ complex {Na(THF) 2 }{Ti[N(C 6 F 5 ) 2 ] 4 } ( 1 ). Single crystal X-ray diffraction studies reveal a tetrahedral titanium center complexed by four decafluorodiphenylamido ligands; while two THF ligands and four fluorine atoms coordinate the sodium cation. ZrCl 4 reacts with 3 equiv. KN(C 6 F 5 ) 2 to give {K(η 6 -C 7 H 8 ) 2 }{ZrCl 2 [N(C 6 F 5 ) 2 ] 3 } ( 2 ). The 19 F NMR spectrum of 2 reveals phenyl resonances in a 2:1 ratio, consistent with a trigonal bipyramidal structure being maintained in solution. The crystal structure of 2 reveals a pseudo-octahedral structure, with the sixth-coordination site being completed by a weak ZrF interaction with a pentafluorophenyl group of an amido ligand. The potassium counterion interacts in an η 6 fashion with two toluene rings in addition to a fluorine atom arising from one of the pentafluorophenyl groups. The reaction of VCl 3 with 3 equiv. KN(C 6 F 5 ) 2 generates the ‘metallate’ complex K{VCl[N(C 6 F 5 ) 2 ] 3 } ( 3 ); the solid state structure of 3 reveals a distorted trigonal bipyramid with the coordination sphere being completed by a weak V–F interaction with the ortho -fluorine of one of the fluorophenyl amido ligands. Exposure of FeCl 3 to 3 equiv. KN(C 6 F 5 ) 2 results in reduction of the metal center and the formation of the Fe(II) species Fe[N(C 6 F 5 ) 2 ] 2 (THF) 2 ( 4 ). Compound 4 is tetrahedral in the solid state with none of the weak MF contacts observed for 1 , 2 , 3 and 5 . CoI 2 reacts with 2 equiv. NaN(C 6 F 5 ) 2 in the presence of pyridine to produce the expected product Co[N(C 6 F 5 ) 2 ] 2 (py) 2 ( 5 ); X-ray crystallography reveals a five-coordinate species in the solid state which is additionally stabilized by a weak CoF interaction.