The molecular structure of tetra-tert-butyldiphosphine: an extremely distorted, sterically crowded molecule
作者： Sarah L Hinchley , Heather E Robertson , Konstantin B Borisenko , Andrew R Turner , Blair F Johnston
DOI: 10.1039/B407908F
关键词: Chemistry 、 Molecule 、 Gas electron diffraction 、 Bond energy 、 Bond-dissociation energy 、 X-ray crystallography 、 Electron diffraction 、 Ab initio 、 Steric effects 、 Crystallography
摘要: The molecular structure of tetra-tert-butyldiphosphine has been determined in the gas phase by electron diffraction using new DYNAMITE method and crystalline X-ray diffraction. Ab initio methods were employed to gain a greater understanding structural preferences this molecule phase, determine intrinsic P–P bond energy, recently described methods. Although is relatively long [GED 226.4(8) pm; 223.4(1) pm] dissociation energy computed be correspondingly small (150.6 kJ mol−1), (258.2 mol−1) normal for diphosphine. gaseous data refined Edinburgh refinement program ed@ed, which detail. P2But4 compared that isoelectronic 1,1,2,2-tetra-tert-butyldisilane. molecules adopt conformation with C2 symmetry. P–P–C angles returned from are 118.8(6) 98.9(6)°, difference 20°, whilst C–P–C angle 110.3(8)°. corresponding parameters crystal 120.9(1), 99.5(1) 109.5(1)°. There also large deformations within tert-butyl groups, making analysis extremely important.
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