Differentially Substituted Acyclic Diaminocarbene Ligands Display Conformation-Dependent Donicities

作者：Collins Mary S; Rosen Evelyn L; Lynch Vincent M; Bielawski Christopher W^*

来源：Organometallics, 2010, 29(13): 3047-3053.

DOI：10.1021/om1004226

Complexes of the type [(L)Ir(COD)Cl] and [(L)Ir(CO)(2)Cl] (L = N,N'-dimesityl-N,N'-dimethylformamidin-2-ylidene (3) and N,N'-bis(2,6-di-isopropylphenyl)-N,N'-dimethylformamidin-2-ylidene (4); COD = cis,cis-1,5-cyclooctadiene) were synthesized and studied in solution as well as in the solid state. While the acyclic diaminocarbene (ADC) ligand in [(3)Ir(COD)Cl] adopted a conformation in which the N-aryl substituents were anti with respect to the coordinated metal, the respective Ir carbonyl complex was prepared as separable isomers ([(anti-3)Ir(CO)(2)Cl] and [(amphi-3)Ir(CO)(2)Cl]). The ADC ligands in [(4)Ir(COD)Cl] and [(4)Ir(CO)(2)Cl] adopted exclusively amphi conformations, where one N-aryl substituent was oriented toward the coordinated metal and the other was oriented away. The Tolman electronic parameter (TEP) for anti-3 (2047.8 cm(-1)) was derived from the carbonyl stretching energy (v(CO)) of the aforementioned Ir(CO)(2)Cl complex and was found to be larger than the TEPs calculated for amphi-3 (2044.4 cm(-1)) and 4(2044.0 cm(-1)). Likewise, the oxidation potential of [(anti-3)Ir(CO)(2)Cl], as measured by cyclic voltammetry, was found to be significantly higher (1.57 V) than the analogous oxidation potentials measured for [(amphi-3)Ir(CO)(2)Cl] (1.26 V) and [(4)Ir(CO)(2)Cl] (1.24 V).

• 出版日期2010-7-12