Conformational analysis of triphenylphosphine in square planar organometallic complexes: [(PPh3)(ML1L2L3)] and [M(acac)(L′)(PPh3)]

被引:14
作者
Conradie, Jeanet [1 ]
机构
[1] Univ Orange Free State, Dept Chem, ZA-9301 Bloemfontein, South Africa
基金
新加坡国家研究基金会;
关键词
IODOMETHANE OXIDATIVE ADDITION; METHYL-IODIDE; PHOSPHINE-LIGANDS; NMR; RH(FCCOCHCOCF(3))(CO)(PPH3); STEREOCHEMISTRY; DERIVATIVES; PRODUCTS; ROTATION; EXCHANGE;
D O I
10.1039/c2dt30850a
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The conformation analysis of free PPh3 and PPh3 coordinated to tetrahedral, trigonal-bipyramidal, octahedral or square planar achiral metal centres is discussed. Results from ADF calculations, in agreement with experimental structures, show that favoured degenerate conformations of complex-bound PPh3 in square planar [(PPh3)((MLLL3)-L-1-L-2)] and [M(acac)(L')(PPh3)] complexes can be obtained by applying the following principles (P helicity, view along P-M axis), (i) superimpose C-ortho of the vertical ring A onto the nadir plane perpendicular to the square plane and allow ring A to tilt towards the smallest ligand, (ii) allow ring B to tilt in the space below the smallest ligand in the quadrant between the nadir plane below the complex and a horizontal plane through the SQP of the complex, (iii) tilt ring C over the largest ligand and (iv) allow correlated tilting of rings A, B and C to minimize inter ring-ring and inter ring-ligand interactions.
引用
收藏
页码:10633 / 10642
页数:10
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