Generation of metal formyl complexes using nickel and platinum hydrides as reducing agents
- National Renewable Energy Lab., Golden, CO (United States)
- Univ. of Colorado, Boulder (United States)
The five-coordinate nickel hydride complex [Ni(dmpe)[sub 2]H]PF[sub 6] (1) [dmpe = 1,2-bis-(dimethylphosphino)ethane] was synthesized by protonation of Ni(dmpe)[sub 2] with NH[sub 4]PF[sub 6]. The platinum analog, [Pt(dmpe)[sub 2]H]PF[sub 6] (2), and [Pt(depe)[sub 2]H]PF[sub 6] (3) [depe = 1, 2-bis(diethylphosphino)ethane]RB were synthesized by reduction of the corresponding Pt(II) complexes with NaBH[sub 4] on alumina. Complexes 1 and 3 can also be synthesized electrochemically. Reduction of Ni-(dmpe)[sub 2][sup 2+] by two electrons in the presence of ammonium ion generates 1, and reduction of Pt(depe)[sub 2][sup 2+] in methanol or wet acetonitrile produces 3. These hydrides react with a variety of cationic metal carbonyl complexes to produce known metal formyl complexes. The structure of 3 was determined by X-ray diffraction. Complex 3 crystallizes in a monoclinic unit cell with P2[sub 1]/c symmetry with a = 14.258 (4) [angstrom], b = 9.648 (3) [angstrom], c = 21.898 (5) [angstrom], [beta] = 91.17 (2)[degrees], V = 3011.7 (14) [degrees][sup 3], Z = 4, and d[sub calcd] = 1.662 g/cm[sup 3]. Full-matrix least-squares refinement converged with residuals R = 4.52% and R[sub w] = 5.90%. 21 refs., 1 fig., 4 tabs.
- OSTI ID:
- 6264010
- Journal Information:
- Organometallics; (United States), Vol. 12:2; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBON MONOXIDE
REDUCTION
NICKEL COMPLEXES
SYNTHESIS
PLATINUM COMPLEXES
AMMONIUM COMPOUNDS
BORON COMPOUNDS
CRYSTALS
ELECTROCHEMISTRY
EXPERIMENTAL DATA
NICKEL HYDRIDES
PLATINUM HYDRIDES
SODIUM COMPOUNDS
X-RAY DIFFRACTION
ALKALI METAL COMPOUNDS
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTIONS
CHEMISTRY
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
NICKEL COMPOUNDS
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
PLATINUM COMPOUNDS
SCATTERING
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
100200* - Synthetic Fuels- Production- (1990-)
400201 - Chemical & Physicochemical Properties
400400 - Electrochemistry