US EPA

1206760 

Journal Article 

GENERATION OF METAL FORMYL COMPLEXES USING NICKEL AND PLATINUM HYDRIDES AS REDUCING AGENTS 

Miedaner, A; Dubois, DL; Curtis, CJ; Haltiwanger, RC 

1993 

1 

Organometallics
ISSN: 0276-7333
EISSN: 1520-6041 

12 

2 

299-303 

WOS:A1993KM31800014 

The five-coordinate nickel hydride complex [Ni(dmpe)2H]PF6, (1) [dmpe = 1,2-bis-(dimethylphosphino)ethane] was synthesized by protonation of Ni(dmpe)2 with NH4PF6. The platinum analog, [Pt(dmpe)2H]PF6 (2), and [Pt(depe)2H]PF6 (3) [depe = 1,2-bis(diethylphos-phino)ethane] were synthesized by reduction of the corresponding Pt(II) complexes with NaBH4 on alumina. Complexes 1 and 3 can also be synthesized electrochemically. Reduction of Ni-(dmpe)2(2+) by two electrons in the presence of ammonium ion generates 1, and reduction of Pt(depe)2(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(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) angstrom3, Z = 4, and d(calcd) = 1.662 g/cm3. Full-matrix least-squares refinement converged with residuals R = 4.52% and R(w) = 5.90%.