Synthesis and structural characterization of ferrocene phosphines modified with polar pendants and their palladium(II) complexes. Part II: N-aminocarbonyl and N-acyl phosphinoferrocene carbohydrazides
Abstract
The reactions of 1'-(diphenylphosphino)-1-(hydrazinylcarbonyl)ferrocene, Ph(2)PfcCONHNH(2) (1; fc = ferrocene-1,1'-diyl), with HNCO, EtNCO, PhNCO, Me2NC(O)Cl/pyridine, and Ac2O/NEt3 produced the corresponding N-functionalized derivatives Ph(2)PfcCONHNHC(O)Y (1a-e), where Y = NH2 (a), NHEt (b), NHPh (c), NMe2 (d), and Me (e). Compounds 1a-e were used as ligands (L) to prepare Pd(II) bis(phosphine) complexes [PdCl2(L-κP)(2)] (3a-e) and two series of Pd(II) complexes bearing an auxiliary 2-[(dimethylamino-κN)methyl]phenyl-κC-1 (L-NC) ligand, namely, [(L-NC)PdCl(L-κP)] (4a-e) and [(L-NC)Pd(L-κO-2,P)][SbF6] (5a-e).
The crystal structures of compounds 1a, 1c, 1e, the phosphine oxide of 1e (i.e., compound 2e), and complexes 3c . 4CH(2)Cl(2) . 2CH(3)OH, 3e . 4CH(3)OH, 4e, and 5e . (2.5)CHCl(3) were determined by single-crystal X-ray diffraction analysis. Hydrogen bonding interactions observed in the solid-state structures of these compounds are discussed.