SYNTHESIS AND CHARACTERIZATION OF WATER-SOLUBLE [PD(TRIPHOSPHINE)(CH3CN)](BF4)(2) COMPLEXES FOR CO2 REDUCTION

被引：66

作者：

HERRING, AM ^{[1
]}

STEFFEY, BD ^{[1
]}

MIEDANER, A ^{[1
]}

WANDER, SA ^{[1
]}

DUBOIS, DL ^{[1
]}

机构：

[1] NATL RENEWABLE ENERGY LAB,GOLDEN,CO 80401

来源：

INORGANIC CHEMISTRY | 1995年 / 34卷 / 05期

关键词：

D O I：

10.1021/ic00109a017

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The syntheses of the triphosphine ligands RP(CH(2)CH(2)PR'(2))(2) (R = CH2CH2CH2OH and R' = Et, HOPetpE; R = Ph and R' = CH2CH2P(O)(OEt)(2), etpEPO; R = Me(2)N and R' = Et, MNetpE; R = i-Pr2N and R' = Et, IPNetpE; R = Ph and R' = NMe(2), etpMN) are described. The reaction of [Pd(CH3CN)(4)(BF4)2 with these ligands forms [Pd(triphosphine)(CH3CN)](BF4)(2) complexes that are all water soluble with the exception of [Pd(IPNetpE)(CH3-CN)](BF4)(2). The labile acetonitrile ligands are easily substituted by triethylphosphine to form [Pd(triphosphine)(PEt(3))](BF4)2 complexes. The triethylphosphine complexes undergo quasi-reversible two-electron reductions while the corresponding acetonitrile complexes undergo two, closely spaced, irreversible, one-electron reductions. [Pd(HoPetpE)(CH3CN)](BF4)(2) and [Pd(etpEPO)(CH3CN)](BF4)(2) are catalysts for the electrochemical reduction of CO2 to CO in both dimethylformamide and buffered aqueous solutions. Kinetic studies are reported for [Pd(HoPetpE)(CH3CN)](BF4)(2) in dimethylformamide.

引用

页码：1100 / 1109

页数：10

共 42 条

[1] CHIRAL SULFONATED PHOSPHINES - SYNTHESES AND USE AS LIGANDS IN ASYMMETRIC HYDROGENATION USING AN AQUEOUS ORGANIC 2-PHASE SOLVENT SYSTEM [J].