(Benzoylacetonato- κ2O,O’)dicarbonyl-rhodium(I)

Abstract
Rhodium compound is an industrial homogeneous catalyst for the processing of organic raw
materials. It is an intriguing metal-organic complex formed by two C atoms from the
carbonyl ligands and the O atoms of the bidentate ligand, known as bcac. The planar C3O2M
chelate ring in the complex is where the two oxygen atoms from the bcac ligand connect to
the rhodium metal core. Delocalized bonding in the monoanionic C3O2 part is compatible
with the aromatic nature of the bcacM ring. Rhodium complexes have gained significant
importance due to their application in catalysis and biological activity.
INTRODUCTION
One of the most extensively used industrial homogeneous catalyst for the processing of
organic raw materials is rhodium compound. Alkene complexes of transition metals continue
to be of interest. The interest stems in part from the fact thar these complexes are crucial for
comprehending the mechanism s underlying transition metal-catalysed homogenous reaction
involving alkenes substrates. (Stuurman, 2007)

Rh(bcac)(CO)₂ is an intriguing metal-organic complex and square-planar geometry observed

around Rh1. Distorted geometry of square-planar coordination. Formed by two C atoms from
the carbonyl ligands and the O atoms of the bidentate ligand. Organization and Cohesion, the
bidentate ligand known as bcac, or benzoylacetonate, is frequently shortened to bcac. BCAc
and the metal ion form six-membered chelate rings in the majority of its complexes. The
planar C₃O₂M chelate ring in the Rh(bcac)(CO)₂ complex is where the two oxygen atoms
from the bcac ligand connect to the rhodium (Rh) metal core. Delocalized bonding in the
monoanionic C₃O₂ part is compatible with the aromatic nature of the bcacM ring. Similar to
electrophilic aromatic substitution, electrophilic substitution events can also happen with the
bcac ligand1. Because it can chelate, the bcac ligand stabilizes metal complexes. Delocalized
π electrons create an aromatic ring in the C ₃O ₂ part of the ligand. The complex's stability is
aided by its aromatic quality.

Since rhodium is essential for so many things, like biological activity and catalysis, it is one
of the transition metals that is researched the most. The small number of rhodium complexes
with sulfur donor ligand are known and the majority of the reported rhodium carbonyl
complexes having metal -sulphur bonds containing alkyl arely, sulphoxide/sulphide ligands
make up the rhodium complexes, which have gained significant important due to their
application in catalysis and biological activity (Singh, 1993).

EXPERIMENT
Refinement
The high Q-peak was selected to be a metal and the ligands were bonded to the metal center.
The ring was refined as the rotating group. All the hydrogens were placed in their parental
carbon. The atoms were refined till the shift became 0.004. all the atoms were made
anisotropic. All the refining of the crystal values are provided on the crystal data table.
Crystal Data
Empirical formula C12H9O4Rh
Formula weight 320.108
Temperature/K 100.01
Crystal system monoclinic
Space group P21/c
a/Å 7.5887(2)
b/Å 6.7522(1)
c/Å 22.5299(5)
α/° 90
β/° 98.850(1)
γ/° 90
3
Volume/Å 1140.70(4)
Z 4

Data collection
ρcalcg/cm3 1.864
-1
μ/mm 1.495
F(000) 627.9
3
Crystal size/mm 0.186 × 0.092 × 0.05
Radiation Mo Kα (λ = 0.71073)
2Θ range for data collection/° 3.66 to 56.6
Index ranges -10 ≤ h ≤ 10, -9 ≤ k ≤ 8, -29 ≤ l ≤ 30
Reflections collected 15332

Refinement
Independent reflections 2824 [Rint = 0.0196, Rsigma = 0.0153]
Data/restraints/parameters 2824/0/155
Goodness-of-fit on F2 1.083
Final R indexes [I>=2σ (I)] R1 = 0.0166, wR2 = 0.0419
Final R indexes [all data] R1 = 0.0201, wR2 = 0.0466
-3
Largest diff. peak/hole / e Å 0.44/-0.41

DISCUSION AND RESULTS

The numbering has been altered for comparison for the three structures.
The determination of bond polarity and formal charge assignment are predicted by
differences in electronegativity among atoms. Bond angles are not greatly impacted by
electronegativity; however, it does affect bond strength.
The bond length between C5 and C6 in structure 1 is longer due to halogen interaction
between fluorine and C6 because fluorine withdrew C6 toward itself. The pi-bond between
O4 and C5 will result in the bond being shorter because of the overlapping of orbitals
resulting in electron density to be more.
Bond angles are more or less the same because the atoms bonded to the metal centre are not
bulky which will result in sterically hindering toward each other and they are not bonded to
electron withdrawing groups.
The torsion angles for some are not present because of the different substituents. The torsion
angle between Rh, O4, C5 and C4 is more on the original structure because rhodium is a
heavy metal and it is bonded to two oxygen and that the methyl is not withdrawing more
electrons but it is donating to the ring resulting in the metal to be heavier. Although
metallophilic interactions can affect bond lengths and angles, torsion angles are not directly
impacted by them as much. The particular molecule structure and the surrounding ligands are
the main determinants of torsion angles. Nonetheless, a molecule's torsional behaviour may
be indirectly impacted by the metallophilic interactions that impact its overall stability.

Table showing bond length of the structures

Atom Atom Original 1 2 3
1.8538(17) 1.8315 1.8513 1.849(3)
Rh1 C2
Rh1 O3 2.0500(12) 2.0425 2.0300 2.0437(17)
Rh1 O4 2.0350(11) 2.0305 2.0295 2.0428(17)
Rh1 C1 1.8479(18) 1.8533 1.8449 1.845(3)
C5 C6 1.503(2) 1.5266 1.5093 1.510(3)
Table 1: Bond Length Å
Table showing bond angles of the structures
Atom Atom Original 1 2 3
C2 Rh O3 92.87(6) 92.18 90.08 90.35
C1 Rh O4 88.53(6) 92.01 90.05 90.06
O4 Rh O3 90.61(5) 89.72 90.05 90.06
C2 Rh C1 88.00(7) 89.18 89.14 88.94
O4 C5 C6 114.95(14) 111.87 116.78 114.97
O3 C3 C7 115.67(14) 115.74 114.94 114.93
Table 2: Bond angles/◦
Table showing torsion angles of the structures
Atom Atom Original 1 2 3
C12C11 C10 -0.06(19) -0.52 -0.95 -
C9
 Rh O4 C5 C4 -1.49(14) -4.00 -0.89 0.62
C7C12 C11 -0.66(18) -0.60 0.44 -
C10
Table 3: Torsion angles/◦

Figure 1: The structure of the molecular components of (I), with displacement

ellipsoids drawn at the 50% probability level

Figure 2: The comparison structure 1 of the molecular components, with displacement

ellipsoids drawn at the 50% probability level
Figure 3: The comparison structure 2 of the molecular components, with displacement
ellipsoids drawn at the 50% probability level

Figure 4: The comparison structure 3 of the molecular components, with displacement

ellipsoids drawn at the 50% probability level
Figure 5: Crystal plane of the title compound with an angle of 26.60˚˚.

Figure 6: Crystal packing of the title compound shown along the b axis.

References
1. Singh, D. K. (1993, April). Rhodium(I) carbonyl complexes with sulphur and nitrogen
donor ligands. 290-292.
2. Stuurman, N. F. (2007). Synthesis, chemical kinetics,thermodynamic and structural
properties of phenyl-containing beta-diketonato complexes of rhodium(I). University
of the Free State, Department of Chemistry. Bloemfontein: University of the Free
State.