Abstract
A symmetrical flexible bis(phosphinoferrocene) derivative, viz. bis[1′-(diphenylphosphino)ferrocenyl]methane (1), was prepared and studied as a ligand in Pd(II) and Au(I) complexes. The reactions of 1 with [PdCl2(cod)] (cod = cycloocta-1,5-diene) and [Pd(μ-Cl)(LNC)]2 (LNC = [2-(dimethylamino-κN)methyl]phenyl-κC1) produced bis(phosphine) complex trans-[PdCl2(1-κ2P,P′)] (4), wherein the ligand spans trans positions in the square-planar coordination sphere of Pd(II) and the tetranuclear, P,P-bridged complex [(μ(P,P′)-1){PdCl(LNC)}2] (5), respectively. In reactions with the Au(I) precursors [AuCl(tht)] and [Au(tht)2][SbF6] (tht = tetrahydrothiophene), ligand 1 gave rise to tetranuclear Au2Fe2 complex [(μ(P,P′)-1)(AuCl)2] (6) and to symmetrical macrocyclic tetramer [Au4(μ(P,P′)-1)4][SbF6]4 (7). All compounds were characterized by spectroscopic methods. In addition, the structures of compound 1, its synthetic precursor bis[1′-(diphenylphosphino)ferrocenyl]methanone (3), and all aforementioned Pd(II) and Au(I) complexes were determined by single-crystal X-ray diffraction analysis (some in solvated form).
Highlights
Phosphinoferrocene ligands have been extensively studied in recent years, for their numerous applications as versatile supporting ligands in coordination chemistry and catalysis [1,2,3,4]
We describe the synthesis of this compound and its coordination behavior towards
Diphosphine 1 was prepared in two steps from 1′-(diphenylphosphino)-1-bromoferrocene
Summary
Phosphinoferrocene ligands have been extensively studied in recent years, for their numerous applications as versatile supporting ligands in coordination chemistry and catalysis [1,2,3,4]. Numerous simple and chiral ferrocene phosphines are available, compounds with two or more connected ferrocene units as the molecular scaffold remain less common. Representative examples of chiral bis(phosphinoferrocene) ligands include BIFEP (I in Scheme 1). Its analogs with various phosphine substituents [5,6], diphosphines from the TRAP family (II) [7,8], and phosphinoferrocenyl analogs of the Trost’s chiral pocket ligand [9] 10 -(phosphino)ferrocenyl units are connected by one- or two-carbon bridges, are so far represented only by compound V. This diphosphine was obtained as a side-product from the reaction of
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