Metallo-selective substitution reactions by amines or phosphines in HRuCo/sub 3/(CO)/sub 12/. IR and /sup 1/H and /sup 59/ NMR studies of HRuCo/sub 3/(CO)/sub 12-x/L/sub x/ (L = amines or phosphines; x = 0-2) and crystal structure of HRuCo/sub 3/ (CO)/sub 11/(PPh/sub 3/)
Reaction of a mixed-metal cluster HRuCo/sub 3/(CO)/sub 12/ with trimethylamine N-oxide or a series of amines leads to the formation of the amine-substituted clusters of the form HRuCo/sub 3/(CO)/sub 11/L (L = NMe/sub 3/, NEt/sub 3/, NMe/sub 2/Ph, rho-H/sub 2/N(C/sub 6/H/sub 4/)NH/sub 2/, 1,4-cyclohexanediamine (1,4-chxn)) in 20-40% yield. The reaction with N,N,N',N'-tetramethylethylenediamine (TMEDA) gives a disubstituted cluster, HRuCo/sub 3/(CO)/sub 10/(TMEDA). IR and /sup 1/H and /sup 59/Co NMR spectra of these clusters indicate that the substitution of amines for the CO ligand takes place preferentially at the ruthenium atom. On the other hand, the reaction with tertiary phosphines gives the phosphine-substituted clusters HRuCo/sub 3/(CO)/sub 12-x/L/sub x/ (L = PPh/sub 3/, x = 1, 2; L = (diphenylphosphino)ethane (dppe), x = 1) in 70-90% yield, where the substitution of phosphines occurs exclusively at the cobalt atom. The structure of HRuCo/sub 3/(CO)/sub 11/(PPh/sub 3/) has been determined by X-ray diffraction. It crystallizes in the space group P2/sub 1//c with a = 11.940 (4) A, b = 17.103 (6) A, c = 17.431 (7) A, ..beta.. = 118.55 (3)/sup 0/, and Z = 4. The cluster has a tetrahedral structure similar to that of the parent HRuCo/sub 3/(CO)/sub 12/ cluster, and the phosphine ligand is axially bonded to one of the three basal cobalt atoms.
- Research Organization:
- Univ. of Tokyo, (Japan)
- OSTI ID:
- 6969961
- Journal Information:
- Organometallics; (United States), Vol. 7:7
- Country of Publication:
- United States
- Language:
- English
Similar Records
Photoelectron spectroscopy and rates of CO substitution of (. eta. sup 5 -C sub 5 H sub 4 X)Rh(CO) sub 2 compounds. Separation of. sigma. and. pi. ring substituent effects
X-ray structural investigation of the pentanuclear carbonyl-phosphine cluster of platinum Pt/sub 5/(CO)(. mu. -/sub 2/-CO)/sub 5/(PPh/sub 3/)/sub 4/ in the form of a solvate with three benzene molecules
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMINES
CHEMICAL REACTIONS
CARBONYLS
CRYSTAL STRUCTURE
PHOSPHINES
RUTHENIUM COMPLEXES
CATALYSTS
COBALT 59
EXPERIMENTAL DATA
HYDROGEN 1
INFRARED SPECTRA
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
SPACE GROUPS
X-RAY DIFFRACTION
COBALT ISOTOPES
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
HYDROGEN ISOTOPES
INFORMATION
INTERMEDIATE MASS NUCLEI
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
PHOSPHORUS COMPOUNDS
RESONANCE
SCATTERING
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties