کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1328642 | 977609 | 2005 | 9 صفحه PDF | دانلود رایگان |

Novel bowl-shaped triarylphosphines, tris(2,2″,6,6″-tetraalkyl[1,1′:3′,1″-terphenyl]-5′-yl)phosphines (TRMP: alkyl = methyl; TRIP: alkyl = isopropyl), were prepared by lithiation of the corresponding m-terphenyl bromides followed by reaction with PCl3. X-ray crystallographic analysis revealed that the phosphorus center of TRMP is embedded in the shallow bowl-shaped cavity of 16 Å diameter and 2.1 Å depth formed by three radially extended m-terphenyl units. Its cone angle was estimated to be as large as 174°. In the crystal structure of TRIP, the depth of the cavity and cone angle increased to 3.3 Å and 206°, respectively, because of the different arrangement of the m-terphenyl units. In contrast with TRMP, which can form the mononuclear complex, PdCl2(TRMP)2 (6), in the reaction with PdCl2, treatment of TRIP (1 or 3 eq.) with PdCl2 produced the trinuclear palladium(II) chloride complex, [(PdCl2)3(TRIP)2] (8), as a single product. X-ray crystallography established the structure of 8, where the trimer of PdCl2 is terminated by two TRIP ligands. The formation of the different types of PdCl2 complexes was explained in terms of the difference in the cavity shape of TRMP and TRIP.
Novel bowl-shaped triarylphosphines, TRMP and TRIP, with large cone angles of 174° and 206°, respectively, were synthesized. The reaction of TRIP with PdCl2 produced the first example of a trinuclear palladium(II) chloride phosphine complex, [(PdCl2)3(TRIP)2], even when an excess amount of TRIP was employed.Figure optionsDownload as PowerPoint slide
Journal: Journal of Organometallic Chemistry - Volume 690, Issue 18, 15 September 2005, Pages 4175–4183