Synthesis, X-ray, crystal structure, and electrochemical properties of the Rh/sub 2//sup 4 +/ complex Rh/sub 2/(form)/sub 4/ (form = N,N'-Di-p-tolylformamidinate anion)
The reaction of the dirhodium(II) mixed-ligand complex Rh/sub 2/(form)/sub 2/(O/sub 2/CCF/sub 3/)/sub 2/(H/sub 2/O) (form = N,N'-di-p-tolylformamidinate anion) with free N,N'-di-p-tolylformamidine (mole ratio 1:4) leads to the formation of the complex Rh/sub 2/ (form)/sub 4/ (1) in excellent yield. The complex was characterized by a single-crystal X-ray diffraction analysis, crystallizing in the space group Pnanti3n, with a = 20.990 (2) A, V = 9248 A/sup 3/, Z = 6, R = 0.036, and R/sub w/ = 0.0378. The Rh-Rh (2.4336 (4) A) and the Rn-N (2.050 (5) A) bond distances are well in the range observed for this class of compounds. The molecule is in a staggered conformation, with N-Rh-Rh-N torsion angles of 16.7 (2)/sup 0/. Complex 1 reacts with carbon monoxide, giving the monocarbonyl adduct Rh/sub 2/-(form)/sub 4/(CO) (2), characterized by elemental analysis and IR, /sup 13/C NMR, and electrochemical measurements. Unlike other dirhodium(II) carbonyl derivatives, 2 is remarkably stable. In the /sup 13/C NMR spectrum a dramatic upfield shift is seen for the carbonyl resonance (delta 144.06); the IR spectrum shows v(CO) at 2040 cm/sup -1/. These data coupled to electrochemical measurements suggest that the ..pi.. back-bonding is reasonably strong in 2. The electrode behavior of 1 has been investigated in different nonaqueous solvents.
- Research Organization:
- Universita di Messina, Italy
- OSTI ID:
- 5522704
- Journal Information:
- Inorg. Chem.; (United States), Vol. 26:14
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMIDES
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
ELECTROCHEMISTRY
RHODIUM COMPLEXES
EXPERIMENTAL DATA
INFRARED SPECTRA
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
SPACE GROUPS
X-RAY DIFFRACTION
CHEMISTRY
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
INFORMATION
MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
RESONANCE
SCATTERING
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400400 - Electrochemistry