Synthesis and Characterization of 2,2-cis-[Rh2(NPhCOCH3)4]•NCC6H4R where R = H, 2-CH3, 3-CH3, 4-CH3 and [Rh2(O2CCH3)(NPhCOCF3)3]

Five novel compounds were synthesized and characterized. Crystal structures were determined using Rigaku Mercury 375/MCCD(XtaLAB mini) diffractometer with graphite monochromated MoKα radiation. The crystal structures of [Rh2(NPhCOCH3)4•xNCC6H4R where x = 1 or 2 and R=H, 2-CH3,3-CH3 and 4-CH3 were solved to an R1 value of less than 5 (R1= Σ||Fo| - |Fc|| / Σ |Fo|). In each of the nitrile complexes, the rhodium is five or six coordinate and possesses pseudo D4h symmetry. The complexes were also characterized by NMR and IR spectroscopy. [Rh2(CO2CCH3)(PhCOCF3)3] was also synthesized. In this complex, each rhodium atom is six coordinate, thus each rhodium is in an octahedral environment. Details of each synthesized complex are discussed

(3-Methylbenzonitrile-1κN)-cis-tetrakis(μ-N-Phenylacetamidato)-1: 2κ\u3csup\u3e4\u3c/sup\u3e N:O;1:2κ\u3csup\u3e4\u3c/sup\u3e O:N-Dirhodium(II)(Rh - Rh)

The complex molecule of the title compound, [Rh2{N(C 6H5)COCH3}4(NCC7H 7)], has crystallographically-imposed mirror symmetry. The four acetamide ligands bridging the dirhodium core are arranged in a 2,2-cis manner with two N atoms and two O atoms coordinating to the unique RhII atom cis to one another. The Neq - Rh - Rh Oeq torsion angles on the acetamide bridge are 0.75(7) and 1.99(9)°. The axial nitrile ligand completes the distorted octahedral coordination sphere of one RhII atom and shows a nonlinear coordination, with an Rh - N - C bond angle of 162.8(5)°; the N - C bond length is 1.154(7)Å

Cis-Tetrakis(μ-N-Phenylacetamidato)-κ\u3csup\u3e4\u3c/sup\u3e N:O;κ\u3csup\u3e4\u3c/sup\u3e O:N-bis[(Benzonitrile-κN)Rhodium(II)](Rh - Rh)

The complex molecule of the title compound, [Rh2{N(C 6H5)COCH3}4(C6H5CN)2], exhibits crystallographically imposed centrosymmetry. The four acetamide ligands bridging the dirhodium core are arranged in a 2,2-cis manner, with two N atoms and two O atoms coordinating to the unique RhII atom cis to one another. The Neq - Rh - Rh - Oeq torsion angles on the acetamide bridges vary between 1.62 (4) and 1.78 (4)°. The Rh - Rh bond length is 2.4319 (3) Å. The axial nitrile ligand completes the distorted octahedral coordination sphere and shows a non-linear coordination with an Rh - N - C bond angle of 167.14 (15)°, while the N - C bond length is 1.135 (3) Å

(3-Methylbenzonitrile-κN)tetrakis(μ-N-phenylacetamidato) -κ\u3csup\u3e4\u3c/sup\u3eN:O;κ\u3csup\u3e4\u3c/sup\u3eO:N-dirhodium(II)(Rh-Rh)

In the title compound, [Rh2(C8H8NO) 4(C8H7N)], the four acetamidate ligands bridging the dirhodium core are arranged in a 2,2-trans manner. One Rh IIatom is five-coordinate, in a distorted pyramidal geometry, while the other is six-coordinate, with a disorted octahedral geometry. For the six-coordinate RhIIatom, the axial nitrile ligand shows a non-linear Rh-nitrile coordination with an Rh-N-C bond angle of 166.4 (4)° and a nitrile N-C bond length of 1.138 (6) Å. Each unique RhIIatom is coordinated by a trans pair of N atoms and a trans pair of O atoms from the four acetamide ligands. The Neq-Rh-Rh-Oeq torsion angles on the acetamide bridge varies between 12.55 (11) and 14.04 (8)°. In the crystal, the 3-methylbenzonitrile ring shows a π-π interaction with an inversion-related equivalent [interplanar spacing = 3.360 (6) Å]. A phenyl ring on one of the acetamide ligands also has a face-to-face π-π interaction with an inversion-related equivalent [interplanar spacing = 3.416 (5) Å]