Carbon dioxide chemistry and electrochemistry of a binuclear cradle complex of Ni(0), Ni/sub 2/(. mu. -CNMe)(CNMe)/sub 2/(PPh/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/
The binuclear Ni(0) complex, Ni/sub 2/(..mu..-CNMe)/sub 2/(CNMe)(dppm)/sub 2/, (1) undergoes two one-electron oxidations (E/sub 1/2/ = -0.51 and -0.83 V vs Ag/AgCl) to form the complex, Ni/sub 2/(..mu..-CNMe)(CNMe)/sub 2/(dppm)/sub 2//sup 2 +/, (2) the crystal structure of 2 as the PF/sub 6//sup -/ salt has been determined. Complex 2 crystallized in the space group P2/sub 1/ with a = 13.659 (3) A, b = 14.852 (4) A, c = 17.970 (3) A, ..beta.. = 101.44 (1)/sup 0/, V = 3573.0 (2) A/sup 3/, and Z = 2. The structure was refined to convergence (R = 0.056, R/sub w/ = 0.073) for 4036 unique data over the range 4/sup 0/ less than or equal to 2 theta less than or equal to 45/sup 0/ by using Mo K..cap alpha.. radiation. Complex 2 exhibits an unusual trans,cis-diphosphine configuration at the Ni centers and contains a semibridging isocyanide. The electrochemical behavior of 2 in the presence of CO/sub 2/ has been examined. Complex 2 reacts with CO/sub 2/ by an EC electrochemical mechanism to afford the CO/sub 2/ complex Ni/sub 2/(..mu..-CNMeCO/sub 2/)(CNMe)/sub 2/(dppm)/sub 2/, (3) complex 3 also has been prepared by reaction of 1 with CO/sub 2/(1). Prolonged reaction of 1 with CO/sub 2/(l) leads to complete carbonylation and Ni/sub 2/(..mu..-CO)(CO)/sub 2/(dppm)/sub 2/, (4) the results of labeling experiments using /sup 13/CO/sub 2/ and 99% /sup 13/C-enriched Ni/sub 2/(..mu..-/sup 13/CNMe)(/sup 13/CNMe)/sub 2/(dppm)/sub 2/ are interpreted in terms of a reaction pathway involving O-atom transfer from CO/sub 2/ to the carbon atom of the bridging isocyanide of 1.
- Research Organization:
- Purdue Univ., West Lafayette, IN
- DOE Contract Number:
- FG22-84PC70791
- OSTI ID:
- 6868572
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 109:3
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
NICKEL COMPLEXES
CRYSTAL STRUCTURE
REDOX REACTIONS
PHOSPHINES
BOND ANGLE
BOND LENGTHS
CARBON DIOXIDE
ELECTROCHEMISTRY
EXPERIMENTAL DATA
INFRARED SPECTRA
LABELLED COMPOUNDS
VOLTAMETRY
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DIMENSIONS
INFORMATION
LENGTH
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
PHOSPHORUS COMPOUNDS
SPECTRA
TRANSITION ELEMENT COMPLEXES
400400* - Electrochemistry