Abstrakt
In order to expand the family of hybrid phosphinoferrocene ligands, a novel phosphinoferrocene sulfonamide ligand, Ph(2)PfcNHSO(2)Me (1, fc = ferrocene-1,1'-diyl), was synthesised through a reaction between P-protected phosphinoamine Ph(2)PfcNH(2). BH3 and MeSO2Cl followed by deprotection of the Ph(2)PfcNHSO(2)Me.
BH3 (2) intermediate. Compound 1 coordinates as a functional phosphine ligand, producing Pd(II) complexes [PdCl(μ-Cl)(1-κP)](2) (4) or [PdCl2(1-κP)(2)] (5) from [PdCl2(cod)] (cod = cycloocta-1,5-diene) depending on the stoichiometry.
The reaction of 1 with [(L-NC)Pd(μ-Cl)](2) also produces a phosphine complex, [(L-NC)PdCl(1-κP)] (6; L-NC = 2-[(dimethylamino-N)methyl]phenyl-κC-1), which was converted into the neutral bis-chelate complex [(L-NC)Pd(Ph(2)PfcNSO(2)Me-κP-2,N)] (7) upon treatment with potassium tert-butoxide; the corresponding cationic chelate [(L-NC)Pd(Ph(2)PfcNHSO(2)Me-κP-2,O)](+) could not be isolated. All compounds were characterised by elemental analysis and spectroscopic methods (NMR, IR and MS).
In addition, the crystal structure of 1, 2, and 4-7 were determined (for solvated compounds in some cases), and the electrochemical properties of 1, 2, 6 and 7 were studied by cyclic voltammetry.