Synthesis of new heteroscorpionate iridium(i) and iridium(iii) complexesElectronic supplementary information (ESI) available: X-ray data for compound 9. CCDC 1012291-1012294. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt00482a

• Main Authors: Roa, A. E, Campos, J, Paneque, M, Salazar, V, Otero, A, Lara-Sánchez, A, Rodríguez, A. M, López-Solera, I, Gómez, M. V
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c5dt00482a

The reactivity of different heteroscorpionate ligands based on bis(pyrazol-1-yl)methane, with different iridium-( i ) and -( iii ) precursors is reported. The reaction of the heteroscorpionate lithium salts "Li(bdmpza)", [bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate], "Li(bdmpzdta)" [bdmpzdta = bis(3,5-dimethylpyrazol-1-yl)dithioacetate] and "Li( S )-mbpam" [( S )-mbpam = ( S )-(-)-N-α-methylbenzyl-2,2-bis(3,5-dimethylpyrazol-1-yl)acetamidate] with 1 equivalent of [IrCl 3 (THF) 3 ] in THF for 18 h affords high yields of neutral and anionic heteroscorpionate chloride iridium complexes [IrCl 2 (bdmpza)(THF)] ( 1 ), [Li(THF) 4 ][IrCl 3 (bdmpzdta)] ( 2 ) and [IrCl 2 {(S)-mbpam})(THF)] ( 3 ). Solution of complex 3 in acetonitrile at room temperature leads to complex [IrCl 2 {(S)-mbpam})(NCCH 3 )] ( 4 ). Complexes 3 and 4 were isolated as enantiopure compounds. The reaction of the lithium salt "Li(bdmpza)" with [IrCl(η 4 -CH 2 &z.dbd;C(Me)C(Me)&z.dbd;CH 2 )] 2 in THF for 18 h gave the Ir( i ) complex [Ir(bdmpza)(η 4 -CH 2 &z.dbd;C(Me)C(Me)&z.dbd;CH 2 )] ( 5 ). The reaction of complex 5 with CO (2 atm) at room temperature leads to a new complex of Ir( iii ), [Ir(bdmpza)(k 2 -CH 2 C(Me)&z.dbd;C(Me)CH 2 )(CO)] ( 6 ). Treatment of heteroscorpionate ligand precursors "Li(bdmpza)" and "Li(bdmpzdta)" with [IrCp*Cl 2 ] 2 in THF yielded the iridium( iii ) complexes [Ir 2 Cp* 2 Cl 2 (bdmpzx)] (x = a 7 , x = dta 8 ). These complexes have helical chirality due to the demands of the fixed pyrazole rings. The stereoisomerism and the self-assembly processes of these helicates have been studied in some detail in solution by NMR spectroscopy and in the solid state by X-ray diffraction. Mixtures of M - and P -handed enantiomers were obtained. Complex 7 undergoes a decarboxylation process initiated by the HCl generated in the previous step leading to the known ionic complex [IrClCp*(bdmpm)][IrCl 3 Cp*] [bdmpm = bis(3,5-dimethylpyrazol-1-yl)methane] ( 9 ). The structures of the complexes were determined by spectroscopic methods and the X-ray crystal structures of 4 , 6 , 8 and 9 were also established. The reactivity of different heteroscorpionate ligands based on bis(pyrazol-1-yl)methane, with different iridium-( i ) and -( iii ) precursors is reported.