EPR study of the oxidation reaction of nickel(0) phosphine complexes with Lewis and Brønsted acids

V. V. Saraev; P. B. Kraikivskii; D. A. Matveev; S. N. Zelinskii; K. Lammertsma

doi:10.1016/j.ica.2006.01.028

EPR study of the oxidation reaction of nickel(0) phosphine complexes with Lewis and Brønsted acids

V. V. Saraev, P. B. Kraikivskii, D. A. Matveev, S. N. Zelinskii, K. Lammertsma

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

15 Citations (Scopus)

Abstract

The oxidation of Ni(PPh₃)₄ with BF₃ · OEt₂, H₃CCOOH, and F₃CCOOH, and that of (PPh₃)₂Ni(C₂H₄) with BF₃ · OEt₂ is studied by EPR spectroscopy. The reaction of the Ni(0) complexes with BF₃ · OEt₂ gives Ni(II) complexes with which they react to form Ni(I) compounds with covalent Ni-F and Ni-B bonds that transform with excess BF₃ · OEt₂ into cationic paramagnetic Ni(I) complexes. Acetic acid also adds oxidatively to Ni(PPh₃)₄ to form a Ni(II) complex that reacts further to give Ni(I) hydride and carboxylate complexes. The Ni(I) hydride is transformed by the acid into the Ni(I) carboxylate with release of hydrogen, the amount of which depends on the rate of acid addition. The following Ni(I) complexes are identified in the reaction medium: [Ni(PPh₃)₃]BF₄, [(PPh₃)₂Ni(OEt₂)]BF₄, [(PPh₃)Ni(OEt₂)_n]BF₄, (PPh₃)₂NiBF₂, (PPh₃)₃NiOOCCH₃, and [(PPh₃)₂Ni(OEt₂)P(OEt)₃]BF₄. Oxidation schemes of Ni(0) complexes by Lewis and Brønsted acids are given.

Original language	English
Pages (from-to)	2314-2320
Number of pages	7
Journal	Inorganica Chimica Acta
Volume	359
Issue number	7
DOIs	https://doi.org/10.1016/j.ica.2006.01.028
Publication status	Published - 25 Apr 2006
Externally published	Yes

Keywords

EPR
Lewis and Brønsted acids
Ni(0) complexes
Ni(I) complexes
Oxidation

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.ica.2006.01.028

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title = "EPR study of the oxidation reaction of nickel(0) phosphine complexes with Lewis and Br{\o}nsted acids",

abstract = "The oxidation of Ni(PPh3)4 with BF3 · OEt2, H3CCOOH, and F3CCOOH, and that of (PPh3)2Ni(C2H4) with BF3 · OEt2 is studied by EPR spectroscopy. The reaction of the Ni(0) complexes with BF3 · OEt2 gives Ni(II) complexes with which they react to form Ni(I) compounds with covalent Ni-F and Ni-B bonds that transform with excess BF3 · OEt2 into cationic paramagnetic Ni(I) complexes. Acetic acid also adds oxidatively to Ni(PPh3)4 to form a Ni(II) complex that reacts further to give Ni(I) hydride and carboxylate complexes. The Ni(I) hydride is transformed by the acid into the Ni(I) carboxylate with release of hydrogen, the amount of which depends on the rate of acid addition. The following Ni(I) complexes are identified in the reaction medium: [Ni(PPh3)3]BF4, [(PPh3)2Ni(OEt2)]BF4, [(PPh3)Ni(OEt2)n]BF4, (PPh3)2NiBF2, (PPh3)3NiOOCCH3, and [(PPh3)2Ni(OEt2)P(OEt)3]BF4. Oxidation schemes of Ni(0) complexes by Lewis and Br{\o}nsted acids are given.",

keywords = "EPR, Lewis and Br{\o}nsted acids, Ni(0) complexes, Ni(I) complexes, Oxidation",

author = "Saraev, {V. V.} and Kraikivskii, {P. B.} and Matveev, {D. A.} and Zelinskii, {S. N.} and K. Lammertsma",

year = "2006",

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TY - JOUR

T1 - EPR study of the oxidation reaction of nickel(0) phosphine complexes with Lewis and Brønsted acids

AU - Saraev, V. V.

AU - Kraikivskii, P. B.

AU - Matveev, D. A.

AU - Zelinskii, S. N.

AU - Lammertsma, K.

PY - 2006/4/25

Y1 - 2006/4/25

N2 - The oxidation of Ni(PPh3)4 with BF3 · OEt2, H3CCOOH, and F3CCOOH, and that of (PPh3)2Ni(C2H4) with BF3 · OEt2 is studied by EPR spectroscopy. The reaction of the Ni(0) complexes with BF3 · OEt2 gives Ni(II) complexes with which they react to form Ni(I) compounds with covalent Ni-F and Ni-B bonds that transform with excess BF3 · OEt2 into cationic paramagnetic Ni(I) complexes. Acetic acid also adds oxidatively to Ni(PPh3)4 to form a Ni(II) complex that reacts further to give Ni(I) hydride and carboxylate complexes. The Ni(I) hydride is transformed by the acid into the Ni(I) carboxylate with release of hydrogen, the amount of which depends on the rate of acid addition. The following Ni(I) complexes are identified in the reaction medium: [Ni(PPh3)3]BF4, [(PPh3)2Ni(OEt2)]BF4, [(PPh3)Ni(OEt2)n]BF4, (PPh3)2NiBF2, (PPh3)3NiOOCCH3, and [(PPh3)2Ni(OEt2)P(OEt)3]BF4. Oxidation schemes of Ni(0) complexes by Lewis and Brønsted acids are given.

AB - The oxidation of Ni(PPh3)4 with BF3 · OEt2, H3CCOOH, and F3CCOOH, and that of (PPh3)2Ni(C2H4) with BF3 · OEt2 is studied by EPR spectroscopy. The reaction of the Ni(0) complexes with BF3 · OEt2 gives Ni(II) complexes with which they react to form Ni(I) compounds with covalent Ni-F and Ni-B bonds that transform with excess BF3 · OEt2 into cationic paramagnetic Ni(I) complexes. Acetic acid also adds oxidatively to Ni(PPh3)4 to form a Ni(II) complex that reacts further to give Ni(I) hydride and carboxylate complexes. The Ni(I) hydride is transformed by the acid into the Ni(I) carboxylate with release of hydrogen, the amount of which depends on the rate of acid addition. The following Ni(I) complexes are identified in the reaction medium: [Ni(PPh3)3]BF4, [(PPh3)2Ni(OEt2)]BF4, [(PPh3)Ni(OEt2)n]BF4, (PPh3)2NiBF2, (PPh3)3NiOOCCH3, and [(PPh3)2Ni(OEt2)P(OEt)3]BF4. Oxidation schemes of Ni(0) complexes by Lewis and Brønsted acids are given.

KW - EPR

KW - Lewis and Brønsted acids

KW - Ni(0) complexes

KW - Ni(I) complexes

KW - Oxidation

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U2 - 10.1016/j.ica.2006.01.028

DO - 10.1016/j.ica.2006.01.028

M3 - Article

AN - SCOPUS:33645856487

SN - 0020-1693

VL - 359

SP - 2314

EP - 2320

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 7

ER -

EPR study of the oxidation reaction of nickel(0) phosphine complexes with Lewis and Brønsted acids

Abstract

Keywords

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