182227-88-9Relevant academic research and scientific papers
Synthesis, Coordination Chemistry and Ligand Properties of Secondary Phosphines R(Ar*)PH with Bulky Aromatic Substituents - Molecular Structure of Ph(2,4,6-iPr3C6H2)PH, (2,4,6-iPr3C6H2)2PH and ClAu[PhP(2,4,6-tBu3C6H2)H]
Brauer, David J.,Bitterer, Frank,D?rrenbach, Frank,He?ler, Gisbert,Stelzer, Othmar,Krüger, Carl,Lutz, Frank
, p. 1183 - 1196 (2007/10/03)
The secondary phosphines R(Ar*)PH (R = Me, iPr, Ph, Mes, Ar*) (2a-2h) with bulky aromatic substituents Ar* (Ar* = 2,3,6-R′3C6H2, R′ = iPr, tBu) are obtained in good yields by reaction of RPCl2, PCl3, PBr3 or Ar*P(Cl,Br)2 with 2,4,6-tBu3C6H2Li or 2,4,6-iPr3C6H2MgBr and subsequent reduction of the intermediate halophosphines R(Ar*)PX (X = Cl, Br) with LiAlH4. The X-ray structural analysis of Ph(2,4,6-iPr3C6H2)PH (2g), space group P1, shows P-C-distances of 1.824(1) and 1.838(1)?. The lithium derivatives of 2a-2c are monomeric in solution as indicated by the 1 : 1 : 1 : 1-quartet 7Li-31P fine structure of the 31P{1H} NMR signals at low temperatures. 2a-2c and 2f-2h form Ni(0) and Fe(0) complexes (CO)3NiL (6a-6f) and Fe(CO)4L (7a-7d), respectively. The Tolman electronic parameters ν of the bulky ligands are almost identical. Within the series 2a-2h the spatial shielding of the P atoms has been estimated using advanced molecular modeling techniques. The bulky ligancl 2c forms coinage metal complexes [Cu(CH3CN)2(2c)2] [PF6] (8). Cu2Cl2(2c)2 (9) and Cl-Au(2c) (10). While 10 is monomeric in solution, in the solid state it forms pairs of head to tail oriented monomers with almost linear Cl-Au-P skeletons (Cl-Au-P 175.47(9)°) as shown by an X-ray structural analysis.
