Unusually Large Bite Angle of a Distally Diphosphanylated Calix[4]arene Chelator

作者：Sameni Soheila; Jeunesse Catherine^*; Awada Mouhamad; Matt Dominique; Welter Richard

来源：European Journal of Inorganic Chemistry, 2010, 2010(31): 4917-4923.

DOI：10.1002/ejic.201000595

• Calixarenes
• Diphosphane
• Nickel
• Silver
• Chelates
• Strained ligands

5,17 -Diphenylphosphanyl-11,23-bis(4-tolyl)-25,26,27,28-tetrapropoxycalix[4]arene (6), a semi-rigid, calixarene-based diphosphane in which the phosphorus atoms are separated by 12 chemical bonds, reacts with [Ni(eta(5)-C(5)H(5))(1,5-cyclooctadiene)]BF(4) or AgBF(4) to afford the corresponding chelate complexes (Ni(eta(5)-C(5)H(5))(6)]BF(4) and [Ag(6)]BF(4) quantitatively. These complexes were both characterised by a single-crystal X-ray diffraction study. In the nickel complex the ligand shows a bite angle of 104.5 degrees, which lies in the range expected for this kind of diphosphane with a large P center dot center dot center dot P separation. In the silver(I) complex the diphosphane displays a much larger bite angle of 138.8 degrees, which was unexpected and reflects the flexilibilty of the calix[4]arene skeleton. Furthermore, in solution the silver complex shows dynamic behaviour. One of the observed motions corresponds to the silver atom switching reversibly from a linear to a bent AgP(2) cordination geometry.

• 出版日期2010-11