Generation of metal formyl complexes using nickel and platinum hydrides as reducing agents

Alex Miedaner, Daniel L DuBois, Calvin J. Curtis, R. Curtis Haltiwanger

Research output: Contribution to journalArticle

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Abstract

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(diethylphospnino)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 P21/c symmetry with a = 14.258 (4) Å, b = 9.648 (3) Å, c= 21.898 (5) Å, β = 91.17 (2)°, V = 3011.7 (14) Å3, Z = 4, and dcalcd = 1.662 g/cm3. Full-matrix least-squares refinement converged with residuals R = 4.52% and Rw = 5.90%.

Original languageEnglish
Pages (from-to)299-303
Number of pages5
JournalOrganometallics
Volume12
Issue number2
Publication statusPublished - 1993

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Reducing Agents
Metal complexes
Platinum
Nickel
Hydrides
hydrides
platinum
Ethane
nickel
ethane
metals
Aluminum Oxide
Protonation
Ammonium Compounds
acetonitrile
Methanol
methyl alcohol
aluminum oxides
Metals
Ions

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Generation of metal formyl complexes using nickel and platinum hydrides as reducing agents. / Miedaner, Alex; DuBois, Daniel L; Curtis, Calvin J.; Haltiwanger, R. Curtis.

In: Organometallics, Vol. 12, No. 2, 1993, p. 299-303.

Research output: Contribution to journalArticle

Miedaner, A, DuBois, DL, Curtis, CJ & Haltiwanger, RC 1993, 'Generation of metal formyl complexes using nickel and platinum hydrides as reducing agents', Organometallics, vol. 12, no. 2, pp. 299-303.
Miedaner, Alex ; DuBois, Daniel L ; Curtis, Calvin J. ; Haltiwanger, R. Curtis. / Generation of metal formyl complexes using nickel and platinum hydrides as reducing agents. In: Organometallics. 1993 ; Vol. 12, No. 2. pp. 299-303.
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abstract = "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(diethylphospnino)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 P21/c symmetry with a = 14.258 (4) {\AA}, b = 9.648 (3) {\AA}, c= 21.898 (5) {\AA}, β = 91.17 (2)°, V = 3011.7 (14) {\AA}3, Z = 4, and dcalcd = 1.662 g/cm3. Full-matrix least-squares refinement converged with residuals R = 4.52{\%} and Rw = 5.90{\%}.",
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N2 - 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(diethylphospnino)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 P21/c symmetry with a = 14.258 (4) Å, b = 9.648 (3) Å, c= 21.898 (5) Å, β = 91.17 (2)°, V = 3011.7 (14) Å3, Z = 4, and dcalcd = 1.662 g/cm3. Full-matrix least-squares refinement converged with residuals R = 4.52% and Rw = 5.90%.

AB - 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(diethylphospnino)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 P21/c symmetry with a = 14.258 (4) Å, b = 9.648 (3) Å, c= 21.898 (5) Å, β = 91.17 (2)°, V = 3011.7 (14) Å3, Z = 4, and dcalcd = 1.662 g/cm3. Full-matrix least-squares refinement converged with residuals R = 4.52% and Rw = 5.90%.

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