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), Journal Name: Organometallics; (United States) Vol. 7:7; ISSN ORGND
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
AMINES
CARBONYLS
CATALYSTS
CHEMICAL REACTIONS
COBALT 59
COBALT ISOTOPES
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
EXPERIMENTAL DATA
HYDROGEN 1
HYDROGEN ISOTOPES
INFORMATION
INFRARED SPECTRA
INTERMEDIATE MASS NUCLEI
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
RESONANCE
RUTHENIUM COMPLEXES
SCATTERING
SPACE GROUPS
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION