B-C bond cleavage of BArF anion upon oxidation of rhodium(I) with AgBArF. Phosphinite rhodium(I), rhodium(II), and rhodium(III) pincer complexes

Hiyam Salem, Linda J W Shimon, Gregory Leitus, Lev Weiner, David Milstein

Research output: Contribution to journalArticle

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Abstract

A rare case of BArF anion cleavage (BArF - = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) by a metal complex is described. Reaction of the Rh(I) dinitrogen complexes 5a,b and 6a,b, based on the phosphinite pincer ligands {C6H4[OP( tBu)2]2} (2), with 2 equiv of AgBArF at room temperature resulted in B-C bond cleavage of one of the BArF anions and aryl transfer to afford the Rh(III) aryl complexes 7 and 8, respectively. The X-ray structure of 8 revealed a square-pyramidal geometry with a coordinated acetone molecule. The aryl transfer occurred as a result of electrophilic attack by unsaturated Rh(III) on one of the aryl rings of the BArF anion. Utilizing different solvents yielded the same product, except when CH3CN was used, in which case one-electron oxidation took place, yielding complex 9. Treatment of 6a,b with 1 equiv of AgX (X = BAr F, BF4, PF6) resulted in a one-electron oxidation to yield the paramagnetic Rh(II) complexes 9-11, respectively. Complex 11 was characterized by X-ray diffraction, revealing a mononuclear square-planar Rh(II) complex.

Original languageEnglish
Pages (from-to)2293-2299
Number of pages7
JournalOrganometallics
Volume27
Issue number10
DOIs
Publication statusPublished - May 26 2008

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Rhodium
rhodium
Anions
cleavage
anions
Oxidation
oxidation
Electrons
Coordination Complexes
Acetone
borates
acetone
attack
electrons
x rays
Ligands
X ray diffraction
X rays
ligands
Molecules

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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B-C bond cleavage of BArF anion upon oxidation of rhodium(I) with AgBArF. Phosphinite rhodium(I), rhodium(II), and rhodium(III) pincer complexes. / Salem, Hiyam; Shimon, Linda J W; Leitus, Gregory; Weiner, Lev; Milstein, David.

In: Organometallics, Vol. 27, No. 10, 26.05.2008, p. 2293-2299.

Research output: Contribution to journalArticle

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abstract = "A rare case of BArF anion cleavage (BArF - = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) by a metal complex is described. Reaction of the Rh(I) dinitrogen complexes 5a,b and 6a,b, based on the phosphinite pincer ligands {C6H4[OP( tBu)2]2} (2), with 2 equiv of AgBArF at room temperature resulted in B-C bond cleavage of one of the BArF anions and aryl transfer to afford the Rh(III) aryl complexes 7 and 8, respectively. The X-ray structure of 8 revealed a square-pyramidal geometry with a coordinated acetone molecule. The aryl transfer occurred as a result of electrophilic attack by unsaturated Rh(III) on one of the aryl rings of the BArF anion. Utilizing different solvents yielded the same product, except when CH3CN was used, in which case one-electron oxidation took place, yielding complex 9. Treatment of 6a,b with 1 equiv of AgX (X = BAr F, BF4, PF6) resulted in a one-electron oxidation to yield the paramagnetic Rh(II) complexes 9-11, respectively. Complex 11 was characterized by X-ray diffraction, revealing a mononuclear square-planar Rh(II) complex.",
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N2 - A rare case of BArF anion cleavage (BArF - = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) by a metal complex is described. Reaction of the Rh(I) dinitrogen complexes 5a,b and 6a,b, based on the phosphinite pincer ligands {C6H4[OP( tBu)2]2} (2), with 2 equiv of AgBArF at room temperature resulted in B-C bond cleavage of one of the BArF anions and aryl transfer to afford the Rh(III) aryl complexes 7 and 8, respectively. The X-ray structure of 8 revealed a square-pyramidal geometry with a coordinated acetone molecule. The aryl transfer occurred as a result of electrophilic attack by unsaturated Rh(III) on one of the aryl rings of the BArF anion. Utilizing different solvents yielded the same product, except when CH3CN was used, in which case one-electron oxidation took place, yielding complex 9. Treatment of 6a,b with 1 equiv of AgX (X = BAr F, BF4, PF6) resulted in a one-electron oxidation to yield the paramagnetic Rh(II) complexes 9-11, respectively. Complex 11 was characterized by X-ray diffraction, revealing a mononuclear square-planar Rh(II) complex.

AB - A rare case of BArF anion cleavage (BArF - = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) by a metal complex is described. Reaction of the Rh(I) dinitrogen complexes 5a,b and 6a,b, based on the phosphinite pincer ligands {C6H4[OP( tBu)2]2} (2), with 2 equiv of AgBArF at room temperature resulted in B-C bond cleavage of one of the BArF anions and aryl transfer to afford the Rh(III) aryl complexes 7 and 8, respectively. The X-ray structure of 8 revealed a square-pyramidal geometry with a coordinated acetone molecule. The aryl transfer occurred as a result of electrophilic attack by unsaturated Rh(III) on one of the aryl rings of the BArF anion. Utilizing different solvents yielded the same product, except when CH3CN was used, in which case one-electron oxidation took place, yielding complex 9. Treatment of 6a,b with 1 equiv of AgX (X = BAr F, BF4, PF6) resulted in a one-electron oxidation to yield the paramagnetic Rh(II) complexes 9-11, respectively. Complex 11 was characterized by X-ray diffraction, revealing a mononuclear square-planar Rh(II) complex.

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