Synthesis and characterization of palladium and nickel complexes with positively charged triphosphine ligands and their use as electrochemical CO2-reduction catalysts

Alex Miedaner; Bruce C. Noll; Daniel L. DuBois

doi:10.1021/om970519c

Synthesis and characterization of palladium and nickel complexes with positively charged triphosphine ligands and their use as electrochemical CO₂-reduction catalysts

Alex Miedaner, Bruce C. Noll, Daniel L. DuBois

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article › peer-review

29 Citations (Scopus)

Abstract

The synthesis and characterization of [M(Bu₃P⁺etpE)Br](BF₄)₂ (where M = Ni or Pd and Bu₃P⁺etpE = [(Bu₃PCH₂CH₂)P(CH₂CH ₂PEt₂)₂]⁺) and [M(etpPBu₃⁺)Br]Br(BF₄)₄ (where M = Ni or Pd and etpPBu₃⁺ = {PhP[CH₂CH₂P(CH₂CH₂PBu ₃)₂]₂}⁴⁺) are described. The structure of [Ni(etpPBu₃⁺)Br]Br(BF₄)₄ has been determined by X-ray diffraction. Treatment of [Pd-(Bu₃P⁺etpE)Br](BF₄)₂ with AgBF₄ in acetonitrile produced [Pd(Bu₃P⁺etpE)(CH₃CN)](BF₄) ₃. The latter compound has also been characterized by single-crystal X-ray diffraction methods. Electrochemical studies indicate that this compound and its closely related methyl analog, [Pd(Me₃P⁺etpE)(CH₃CN)](BF₄) ₃, are catalysts for the electrochemical reduction of CO₂ to CO in acidic dimethylformamide solutions. Kinetic and mechanistic studies of this catalytic reaction are reported.

Original language	English
Pages (from-to)	5779-5791
Number of pages	13
Journal	Organometallics
Volume	16
Issue number	26
DOIs	https://doi.org/10.1021/om970519c
Publication status	Published - Dec 23 1997

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

Access to Document

10.1021/om970519c

Fingerprint Dive into the research topics of 'Synthesis and characterization of palladium and nickel complexes with positively charged triphosphine ligands and their use as electrochemical CO<sub>2</sub>-reduction catalysts'. Together they form a unique fingerprint.

Cite this

@article{c802e74ee90442f3b43014724cc73524,

title = "Synthesis and characterization of palladium and nickel complexes with positively charged triphosphine ligands and their use as electrochemical CO2-reduction catalysts",

abstract = "The synthesis and characterization of [M(Bu3P+etpE)Br](BF4)2 (where M = Ni or Pd and Bu3P+etpE = [(Bu3PCH2CH2)P(CH2CH 2PEt2)2]+) and [M(etpPBu3+)Br]Br(BF4)4 (where M = Ni or Pd and etpPBu3+ = {PhP[CH2CH2P(CH2CH2PBu 3)2]2}4+) are described. The structure of [Ni(etpPBu3+)Br]Br(BF4)4 has been determined by X-ray diffraction. Treatment of [Pd-(Bu3P+etpE)Br](BF4)2 with AgBF4 in acetonitrile produced [Pd(Bu3P+etpE)(CH3CN)](BF4) 3. The latter compound has also been characterized by single-crystal X-ray diffraction methods. Electrochemical studies indicate that this compound and its closely related methyl analog, [Pd(Me3P+etpE)(CH3CN)](BF4) 3, are catalysts for the electrochemical reduction of CO2 to CO in acidic dimethylformamide solutions. Kinetic and mechanistic studies of this catalytic reaction are reported.",

author = "Alex Miedaner and Noll, {Bruce C.} and DuBois, {Daniel L.}",

year = "1997",

month = dec,

day = "23",

doi = "10.1021/om970519c",

language = "English",

volume = "16",

pages = "5779--5791",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "26",

}

TY - JOUR

T1 - Synthesis and characterization of palladium and nickel complexes with positively charged triphosphine ligands and their use as electrochemical CO2-reduction catalysts

AU - Miedaner, Alex

AU - Noll, Bruce C.

AU - DuBois, Daniel L.

PY - 1997/12/23

Y1 - 1997/12/23

N2 - The synthesis and characterization of [M(Bu3P+etpE)Br](BF4)2 (where M = Ni or Pd and Bu3P+etpE = [(Bu3PCH2CH2)P(CH2CH 2PEt2)2]+) and [M(etpPBu3+)Br]Br(BF4)4 (where M = Ni or Pd and etpPBu3+ = {PhP[CH2CH2P(CH2CH2PBu 3)2]2}4+) are described. The structure of [Ni(etpPBu3+)Br]Br(BF4)4 has been determined by X-ray diffraction. Treatment of [Pd-(Bu3P+etpE)Br](BF4)2 with AgBF4 in acetonitrile produced [Pd(Bu3P+etpE)(CH3CN)](BF4) 3. The latter compound has also been characterized by single-crystal X-ray diffraction methods. Electrochemical studies indicate that this compound and its closely related methyl analog, [Pd(Me3P+etpE)(CH3CN)](BF4) 3, are catalysts for the electrochemical reduction of CO2 to CO in acidic dimethylformamide solutions. Kinetic and mechanistic studies of this catalytic reaction are reported.

AB - The synthesis and characterization of [M(Bu3P+etpE)Br](BF4)2 (where M = Ni or Pd and Bu3P+etpE = [(Bu3PCH2CH2)P(CH2CH 2PEt2)2]+) and [M(etpPBu3+)Br]Br(BF4)4 (where M = Ni or Pd and etpPBu3+ = {PhP[CH2CH2P(CH2CH2PBu 3)2]2}4+) are described. The structure of [Ni(etpPBu3+)Br]Br(BF4)4 has been determined by X-ray diffraction. Treatment of [Pd-(Bu3P+etpE)Br](BF4)2 with AgBF4 in acetonitrile produced [Pd(Bu3P+etpE)(CH3CN)](BF4) 3. The latter compound has also been characterized by single-crystal X-ray diffraction methods. Electrochemical studies indicate that this compound and its closely related methyl analog, [Pd(Me3P+etpE)(CH3CN)](BF4) 3, are catalysts for the electrochemical reduction of CO2 to CO in acidic dimethylformamide solutions. Kinetic and mechanistic studies of this catalytic reaction are reported.

UR - http://www.scopus.com/inward/record.url?scp=0000834978&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000834978&partnerID=8YFLogxK

U2 - 10.1021/om970519c

DO - 10.1021/om970519c

M3 - Article

AN - SCOPUS:0000834978

VL - 16

SP - 5779

EP - 5791

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 26

ER -