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

Abstract

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.

Authors:
; ;  [1];  [2]
  1. National Renewable Energy Lab., Golden, CO (United States)
  2. Univ. of Colorado, Boulder (United States)
Publication Date:
OSTI Identifier:
6264010
Resource Type:
Journal Article
Journal Name:
Organometallics; (United States)
Additional Journal Information:
Journal Volume: 12:2; Journal ID: ISSN 0276-7333
Country of Publication:
United States
Language:
English
Subject:
10 SYNTHETIC FUELS; 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

Citation Formats

Miedaner, A, DuBois, D L, Curtis, C J, and Haltiwanger, R C. Generation of metal formyl complexes using nickel and platinum hydrides as reducing agents. United States: N. p., 1993. Web. doi:10.1021/om00026a014.
Miedaner, A, DuBois, D L, Curtis, C J, & Haltiwanger, R C. Generation of metal formyl complexes using nickel and platinum hydrides as reducing agents. United States. https://doi.org/10.1021/om00026a014
Miedaner, A, DuBois, D L, Curtis, C J, and Haltiwanger, R C. 1993. "Generation of metal formyl complexes using nickel and platinum hydrides as reducing agents". United States. https://doi.org/10.1021/om00026a014.
@article{osti_6264010,
title = {Generation of metal formyl complexes using nickel and platinum hydrides as reducing agents},
author = {Miedaner, A and DuBois, D L and Curtis, C J and Haltiwanger, R C},
abstractNote = {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.},
doi = {10.1021/om00026a014},
url = {https://www.osti.gov/biblio/6264010}, journal = {Organometallics; (United States)},
issn = {0276-7333},
number = ,
volume = 12:2,
place = {United States},
year = {1993},
month = {2}
}