In:
Zeitschrift für Naturforschung B, Walter de Gruyter GmbH, Vol. 51, No. 8 ( 1996-8-1), p. 1183-1196
Abstract:
The secondary phosphines R(Ar*)PH(R = Me, iPr, Ph, Mes, Ar*) (2a-2h) with bulky aromatic substituents Ar* (Ar* = 2,3,6-R′ 3 C 6 H 2 , R′ = iPr, tBu) are obtained in good yields by reaction of RPCl 2 , PCl 3 , PBr 3 or Ar*P(Cl, Br) 2 with 2,4,6-tBu 3 C 6 H 2 Li or 2,4,6- iPr 3 C 6 H 2 MgBr and subsequent reduction of the intermediate halophosphines R(Ar*)PX(X = Cl, Br) with LiAlH 4 . The X-ray structural analysis of Ph(2,4,6-iPr 3 C 6 H 2 )PH (2g), space group P 1 , shows P-C-distances of 1.824(1) and 1.838(1)Å. The lithium derivatives of 2a-2c are monomeric in solution as indicated by the 1 :1 :1 : 1-quartet 7 L i - 31 P fine structure of the 31 P {1H} NMR signals at low temperatures. 2a-2c and 2f-2h form Ni(0) and Fe(0) complexes (CO) 3 NiL (6a-6f) and Fe(CO) 4 L (7a-7d), respectively. The Tolman electronic parameters 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 ligand 2c forms coinage metal complexes [C u(CH 3 CN) 2 (2c) 2 ] [PF 6 ] (8), Cu 2 Cl 2 (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.
Type of Medium:
Online Resource
ISSN:
1865-7117
,
0932-0776
DOI:
10.1515/znb-1996-0819
Language:
English
Publisher:
Walter de Gruyter GmbH
Publication Date:
1996
detail.hit.zdb_id:
2078109-X
detail.hit.zdb_id:
124635-5
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