Abstract
The crystal structure of [Rh(PhCOCHCO(CH2)3CH 3)(CO)(PPh3)], 1, and the conformation analysis of PPh3 coordinated to 1 is presented. Two geometrical isomers are possible, which unexpectedly crystallized in the same space in the unit cell with an 89.7:10.3 ratio. Results from density functional theory calculations, in agreement with experimental structures, show that favored degenerate conformations of coordinated PPh3 in square planar [(PPh 3)(ML1L2L3)], [M(acac)(L')(PPh 3)] and [Rh(β-diketonato)(CO)(PPh3)] complexes possess distinct features and can be obtained by applying the following principles (P helicity, view along P-M axis), (i) superimpose Co 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. The steric influence of Oβ-diketonato and CO is similar on the preferred orientation of the vertical phenyl ring A of PPh3 in [Rh(β-diketonato)(CO)(PPh3)] complexes. The size of the side groups R and R′ on the β-diketonato ligand (RCOCHCOR′) - does not influence the preferred conformation of coordinated PPh3 in [Rh(β-diketonato)(CO)(PPh3)].
Original language | English |
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Pages (from-to) | 237-244 |
Number of pages | 8 |
Journal | Inorganica Chimica Acta |
Volume | 395 |
DOIs | |
Publication status | Published - 30 Jan 2013 |
Keywords
- Conformation
- DFT
- Rhodium
- Square planar
- Triphenylphosphine
- β-Diketone
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry