Synthesis, Coordination and Electrochemistry of a Ferrocenyl‐Tagged Aminobisphosphane Ligand

Abstract

Introducing a ferrocene moiety into a molecule results in the incorporation of a metal center and a redox active moiety. This contribution describes the synthesis of FcN(CH 2 PPh 2 ) 2 (1; Fc = ferrocenyl), a ferrocene analog of the widely studied bisphosphane pincer ligands, RN(CH 2 PPh 2 ) 2 . Compound 1 was studied as a ligand in complexes of Group 10 and 11 metal ions. The following compounds were synthesized and characterized using a combination of spectroscopic methods and single-crystal X-ray diffraction analysis: the square planar complexes [MX 2 (1-k 2 P,P')] (M/X = Ni/Cl, Pd/Cl, Pd/Br, Pd/I and Pt/ Cl) and the tetrahedral complexes [M(1-k 2 P,P') 2 ]X (M/X = Cu/PF 6 , Ag/SbF 6 and Au/SbF 6 ). Furthermore, a pair of open and cyclic digold(I) complexes containing bis-phosphane 1 as a P,Pbridging ligand, viz. [(μ(P,P')-1)(AuCl) 2 ] and [(μ(P,P')-1) 2 Au 2 ][SbF 6 ] 2 , were isolated. Ligand 1, the corresponding phosphane selenide 1-Se and all complexes (except for the poorly soluble [(μ(P,P')-1) 2 Au 2 ][SbF 6 ] and unstable [Ag(1k 2 P,P') 2 ][SbF 6 ]) were further analyzed by cyclic voltammetry.

Transition Metal Complexes of 2,6‐Dibenzhydryl Derived Bisphosphine: Synthesis, Structural Studies and Palladium Complex Promoted Suzuki‐Miyaura Reactions

“…The metal centres in 4 and 5 adopt slightly distorted square planar geometries as supported by the ∠Cl−Pd−P bond angles in 4 (86.79(3)° and 88.99(3)°) and ∠Cl−Pt−P bond angles in 5 (92.01(3)° and 87.91(2)°). The ∠P1−M1−P2 bite angles of 91.38(3)° for 4 and 92.26(2)° for 5 , are considerably shorter than the same found in analogous complexes [{2,6‐{PPh 2 C 3 H 2 N 2 } 2 C 5 H 3 N}{MCl 2 } ‐κ 2 ‐P , P ] [M=Pd; 102.43(4)°, M=Pt; 104.07(2)°] [14] and [{(C 5 H 5 ) 2 Fe}N(CH 2 PPh 2 ) 2 (MCl 2 ) ‐κ 2 ‐P , P ] [ M=Pd; 94.53(4)°, M=Pt; 95.92(3)°] [9b] . The Pd−P bond distances in 4 [2.2398(9) Å and 2.2260(9) Å] are shorter than those found in complexes [PdCl 2 (Xantphos)] [15] (Pd−P avg 2.295(3) Å) and [PdCl 2 (dppf)] [16] (Pd−P avg 2.292(3) Å) and [PdCl 2 (dppp)] [17] (Pd−P avg 2.244(1) Å) [18] .…”

The Backbone of Success of P,N-Hybrid Ligands: Some Recent Developments

“…π interactions upon complexation to Group 11 metal centres [105]. The air stable orange ferrocenyl bisphosphinoamine 6j could be prepared, in 87% yield, from double condensation of the ferrocenyl primary amine and Ph 2 PCH 2 OH and showed a 31 P signal at −23.5 ppm [106]. The X-ray structure of this compound was also determined.…”