Oxidative addition of a diphosphine anhydride to iron(0) and nickel(0): A simple approach to installing four ligands

Mark R. Ringenberg; Danielle L. Gray; Thomas B. Rauchfuss

doi:10.1021/om200073k

Oxidative addition of a diphosphine anhydride to iron(0) and nickel(0): A simple approach to installing four ligands

Mark R. Ringenberg, Danielle L. Gray, Thomas B. Rauchfuss

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

Abstract

The diphosphine anhydride (PCO)₂O was prepared in high yield by DCC coupling of 2-diphenylphosphinobenzoic acid. The diphosphine oxidatively adds to Fe(0) carbonyls to give the acyl carboxylate Fe(PCO)(PCO ₂)(CO)₂ (1). The complex adopts a distorted octahedral geometry with trans phosphines and cis carbonyl ligands. Treatment of Ni(COD)₂ with (PCO)₂O afforded the square-planar acyl carboxylate Ni(PCO)(PCO₂) (2) with trans phosphine ligands. Upon treatment with PMe₃, 1 gives the monocarbonyl Fe(PCO)(PCO ₂)(CO)(PMe₃), whereas 2 and PMe₃ react to give the pentacoordinate adduct 2PMe₃. Both 1 and 2 give 1:1 adducts with B(C₆F₅)₃ (BPh^F₃). Crystallographic analysis revealed that the borane binds to the noncoordinated carboxylate oxygen in both cases. The value of ν_CO for the carboxylato ligand decreased by 45 cm^-1, and in the case of 1BPh ^F₃, ν_CO for the CO ligands increased by 15 cm^-1. In solution, 1BPh^F₃ exists as an equilibrium mixture of three isomers, including a kinetic isomer and another isomer that selectively crystallizes.

Original language	English (US)
Pages (from-to)	2885-2888
Number of pages	4
Journal	Organometallics
Volume	30
Issue number	10
DOIs	https://doi.org/10.1021/om200073k
State	Published - May 23 2011

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Oxidative addition of a diphosphine anhydride to iron(0) and nickel(0): A simple approach to installing four ligands",

abstract = "The diphosphine anhydride (PCO)2O was prepared in high yield by DCC coupling of 2-diphenylphosphinobenzoic acid. The diphosphine oxidatively adds to Fe(0) carbonyls to give the acyl carboxylate Fe(PCO)(PCO 2)(CO)2 (1). The complex adopts a distorted octahedral geometry with trans phosphines and cis carbonyl ligands. Treatment of Ni(COD)2 with (PCO)2O afforded the square-planar acyl carboxylate Ni(PCO)(PCO2) (2) with trans phosphine ligands. Upon treatment with PMe3, 1 gives the monocarbonyl Fe(PCO)(PCO 2)(CO)(PMe3), whereas 2 and PMe3 react to give the pentacoordinate adduct 2PMe3. Both 1 and 2 give 1:1 adducts with B(C6F5)3 (BPhF3). Crystallographic analysis revealed that the borane binds to the noncoordinated carboxylate oxygen in both cases. The value of νCO for the carboxylato ligand decreased by 45 cm-1, and in the case of 1BPh F3, νCO for the CO ligands increased by 15 cm-1. In solution, 1BPhF3 exists as an equilibrium mixture of three isomers, including a kinetic isomer and another isomer that selectively crystallizes.",

author = "Ringenberg, {Mark R.} and Gray, {Danielle L.} and Rauchfuss, {Thomas B.}",

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AU - Rauchfuss, Thomas B.

PY - 2011/5/23

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N2 - The diphosphine anhydride (PCO)2O was prepared in high yield by DCC coupling of 2-diphenylphosphinobenzoic acid. The diphosphine oxidatively adds to Fe(0) carbonyls to give the acyl carboxylate Fe(PCO)(PCO 2)(CO)2 (1). The complex adopts a distorted octahedral geometry with trans phosphines and cis carbonyl ligands. Treatment of Ni(COD)2 with (PCO)2O afforded the square-planar acyl carboxylate Ni(PCO)(PCO2) (2) with trans phosphine ligands. Upon treatment with PMe3, 1 gives the monocarbonyl Fe(PCO)(PCO 2)(CO)(PMe3), whereas 2 and PMe3 react to give the pentacoordinate adduct 2PMe3. Both 1 and 2 give 1:1 adducts with B(C6F5)3 (BPhF3). Crystallographic analysis revealed that the borane binds to the noncoordinated carboxylate oxygen in both cases. The value of νCO for the carboxylato ligand decreased by 45 cm-1, and in the case of 1BPh F3, νCO for the CO ligands increased by 15 cm-1. In solution, 1BPhF3 exists as an equilibrium mixture of three isomers, including a kinetic isomer and another isomer that selectively crystallizes.

AB - The diphosphine anhydride (PCO)2O was prepared in high yield by DCC coupling of 2-diphenylphosphinobenzoic acid. The diphosphine oxidatively adds to Fe(0) carbonyls to give the acyl carboxylate Fe(PCO)(PCO 2)(CO)2 (1). The complex adopts a distorted octahedral geometry with trans phosphines and cis carbonyl ligands. Treatment of Ni(COD)2 with (PCO)2O afforded the square-planar acyl carboxylate Ni(PCO)(PCO2) (2) with trans phosphine ligands. Upon treatment with PMe3, 1 gives the monocarbonyl Fe(PCO)(PCO 2)(CO)(PMe3), whereas 2 and PMe3 react to give the pentacoordinate adduct 2PMe3. Both 1 and 2 give 1:1 adducts with B(C6F5)3 (BPhF3). Crystallographic analysis revealed that the borane binds to the noncoordinated carboxylate oxygen in both cases. The value of νCO for the carboxylato ligand decreased by 45 cm-1, and in the case of 1BPh F3, νCO for the CO ligands increased by 15 cm-1. In solution, 1BPhF3 exists as an equilibrium mixture of three isomers, including a kinetic isomer and another isomer that selectively crystallizes.

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Oxidative addition of a diphosphine anhydride to iron(0) and nickel(0): A simple approach to installing four ligands

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