Ortho phosphorylation of PPh3 to give a diphosphine and formation of a "butterfly" structure on a tetrairidium framework

Bo Keun Park, Md Arzu Miah, Hongkyu Kang, Kwangyeol Lee, Youn Jaung Cho, David G. Churchill, Sangwoo Park, Moon Gun Choi, Joon T. Park

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

A brief thermolysis of the bis-phosphine-substituted tetrairidium cluster Ir4(CO)10(PPh3)2 (1) in chlorobenzene (CB) converts it rapidly to the diphosphine cluster Ir 4(CO)7(μ-CO)32-Ph 2P(o-C6H4)PPh2} (2) in 53% yield, providing evidence for ortho phosphorylation at the tetrairidium cluster framework. Treatment of 2 with excess C60 affords the "butterfly" Ir4-C60 complex Ir 4(CO)6)(μ-CO){μ32- Ph2P(o-C6H4)P(η1-o-C 6H4)}(μ32: η2η2-c60 (3) in 71% yield. Interestingly, compound 3 can be prepared directly from the thermolysis of 1 with excess C60 in moderate yield (52%). Compounds 2 and 3 have been characterized by micro-analysis, spectroscopy, and single-crystal X-ray diffraction studies. A molecular structure determination reveals that complex 2 adopts a regular tetrahedral geometry with three edge-bridging CO groups around the basal triangle and a diphosphine κ2-Ph2P(o- C6H4)PPh2 ligand chelating one of the basal iridium atoms. In contrast, complex 3 possesses a "butterfly" geometry in which the C60 ligand is coordinated to the lower wing of the "butterfly" by an arene type μ32: η22-C60 bonding mode. One unique feature of 3 is the presence of both ortho phosphorylated and ortho-metalated phenyl rings forming five-membered [Ir-P-C-C-P] and [Ir-Ir-P-C-C] metallocycles joined in a spiro union at the iridium-indium-bridged phosphorus atom. A crossover experiment confirms that the conversion of 1 to 2 is intramolecular. Plausible reaction pathways for the formation of 2 and 3 are proposed.

Original languageEnglish
Pages (from-to)675-679
Number of pages5
JournalOrganometallics
Volume24
Issue number4
DOIs
Publication statusPublished - 2005 Feb 14
Externally publishedYes

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phosphorylation
Phosphorylation
Carbon Monoxide
iridium
Iridium
Thermolysis
phosphine
unions
ligands
chlorobenzenes
geometry
microanalysis
phosphines
triangles
wings
indium
atoms
phosphorus
crossovers
Ligands

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Ortho phosphorylation of PPh3 to give a diphosphine and formation of a "butterfly" structure on a tetrairidium framework. / Park, Bo Keun; Miah, Md Arzu; Kang, Hongkyu; Lee, Kwangyeol; Cho, Youn Jaung; Churchill, David G.; Park, Sangwoo; Choi, Moon Gun; Park, Joon T.

In: Organometallics, Vol. 24, No. 4, 14.02.2005, p. 675-679.

Research output: Contribution to journalArticle

Park, BK, Miah, MA, Kang, H, Lee, K, Cho, YJ, Churchill, DG, Park, S, Choi, MG & Park, JT 2005, 'Ortho phosphorylation of PPh3 to give a diphosphine and formation of a "butterfly" structure on a tetrairidium framework', Organometallics, vol. 24, no. 4, pp. 675-679. https://doi.org/10.1021/om049303i
Park, Bo Keun ; Miah, Md Arzu ; Kang, Hongkyu ; Lee, Kwangyeol ; Cho, Youn Jaung ; Churchill, David G. ; Park, Sangwoo ; Choi, Moon Gun ; Park, Joon T. / Ortho phosphorylation of PPh3 to give a diphosphine and formation of a "butterfly" structure on a tetrairidium framework. In: Organometallics. 2005 ; Vol. 24, No. 4. pp. 675-679.
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title = "Ortho phosphorylation of PPh3 to give a diphosphine and formation of a {"}butterfly{"} structure on a tetrairidium framework",
abstract = "A brief thermolysis of the bis-phosphine-substituted tetrairidium cluster Ir4(CO)10(PPh3)2 (1) in chlorobenzene (CB) converts it rapidly to the diphosphine cluster Ir 4(CO)7(μ-CO)3{κ2-Ph 2P(o-C6H4)PPh2} (2) in 53{\%} yield, providing evidence for ortho phosphorylation at the tetrairidium cluster framework. Treatment of 2 with excess C60 affords the {"}butterfly{"} Ir4-C60 complex Ir 4(CO)6)(μ-CO){μ3-κ2- Ph2P(o-C6H4)P(η1-o-C 6H4)}(μ3-η2: η2η2-c60 (3) in 71{\%} yield. Interestingly, compound 3 can be prepared directly from the thermolysis of 1 with excess C60 in moderate yield (52{\%}). Compounds 2 and 3 have been characterized by micro-analysis, spectroscopy, and single-crystal X-ray diffraction studies. A molecular structure determination reveals that complex 2 adopts a regular tetrahedral geometry with three edge-bridging CO groups around the basal triangle and a diphosphine κ2-Ph2P(o- C6H4)PPh2 ligand chelating one of the basal iridium atoms. In contrast, complex 3 possesses a {"}butterfly{"} geometry in which the C60 ligand is coordinated to the lower wing of the {"}butterfly{"} by an arene type μ3-η2: η2:η2-C60 bonding mode. One unique feature of 3 is the presence of both ortho phosphorylated and ortho-metalated phenyl rings forming five-membered [Ir-P-C-C-P] and [Ir-Ir-P-C-C] metallocycles joined in a spiro union at the iridium-indium-bridged phosphorus atom. A crossover experiment confirms that the conversion of 1 to 2 is intramolecular. Plausible reaction pathways for the formation of 2 and 3 are proposed.",
author = "Park, {Bo Keun} and Miah, {Md Arzu} and Hongkyu Kang and Kwangyeol Lee and Cho, {Youn Jaung} and Churchill, {David G.} and Sangwoo Park and Choi, {Moon Gun} and Park, {Joon T.}",
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T1 - Ortho phosphorylation of PPh3 to give a diphosphine and formation of a "butterfly" structure on a tetrairidium framework

AU - Park, Bo Keun

AU - Miah, Md Arzu

AU - Kang, Hongkyu

AU - Lee, Kwangyeol

AU - Cho, Youn Jaung

AU - Churchill, David G.

AU - Park, Sangwoo

AU - Choi, Moon Gun

AU - Park, Joon T.

PY - 2005/2/14

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N2 - A brief thermolysis of the bis-phosphine-substituted tetrairidium cluster Ir4(CO)10(PPh3)2 (1) in chlorobenzene (CB) converts it rapidly to the diphosphine cluster Ir 4(CO)7(μ-CO)3{κ2-Ph 2P(o-C6H4)PPh2} (2) in 53% yield, providing evidence for ortho phosphorylation at the tetrairidium cluster framework. Treatment of 2 with excess C60 affords the "butterfly" Ir4-C60 complex Ir 4(CO)6)(μ-CO){μ3-κ2- Ph2P(o-C6H4)P(η1-o-C 6H4)}(μ3-η2: η2η2-c60 (3) in 71% yield. Interestingly, compound 3 can be prepared directly from the thermolysis of 1 with excess C60 in moderate yield (52%). Compounds 2 and 3 have been characterized by micro-analysis, spectroscopy, and single-crystal X-ray diffraction studies. A molecular structure determination reveals that complex 2 adopts a regular tetrahedral geometry with three edge-bridging CO groups around the basal triangle and a diphosphine κ2-Ph2P(o- C6H4)PPh2 ligand chelating one of the basal iridium atoms. In contrast, complex 3 possesses a "butterfly" geometry in which the C60 ligand is coordinated to the lower wing of the "butterfly" by an arene type μ3-η2: η2:η2-C60 bonding mode. One unique feature of 3 is the presence of both ortho phosphorylated and ortho-metalated phenyl rings forming five-membered [Ir-P-C-C-P] and [Ir-Ir-P-C-C] metallocycles joined in a spiro union at the iridium-indium-bridged phosphorus atom. A crossover experiment confirms that the conversion of 1 to 2 is intramolecular. Plausible reaction pathways for the formation of 2 and 3 are proposed.

AB - A brief thermolysis of the bis-phosphine-substituted tetrairidium cluster Ir4(CO)10(PPh3)2 (1) in chlorobenzene (CB) converts it rapidly to the diphosphine cluster Ir 4(CO)7(μ-CO)3{κ2-Ph 2P(o-C6H4)PPh2} (2) in 53% yield, providing evidence for ortho phosphorylation at the tetrairidium cluster framework. Treatment of 2 with excess C60 affords the "butterfly" Ir4-C60 complex Ir 4(CO)6)(μ-CO){μ3-κ2- Ph2P(o-C6H4)P(η1-o-C 6H4)}(μ3-η2: η2η2-c60 (3) in 71% yield. Interestingly, compound 3 can be prepared directly from the thermolysis of 1 with excess C60 in moderate yield (52%). Compounds 2 and 3 have been characterized by micro-analysis, spectroscopy, and single-crystal X-ray diffraction studies. A molecular structure determination reveals that complex 2 adopts a regular tetrahedral geometry with three edge-bridging CO groups around the basal triangle and a diphosphine κ2-Ph2P(o- C6H4)PPh2 ligand chelating one of the basal iridium atoms. In contrast, complex 3 possesses a "butterfly" geometry in which the C60 ligand is coordinated to the lower wing of the "butterfly" by an arene type μ3-η2: η2:η2-C60 bonding mode. One unique feature of 3 is the presence of both ortho phosphorylated and ortho-metalated phenyl rings forming five-membered [Ir-P-C-C-P] and [Ir-Ir-P-C-C] metallocycles joined in a spiro union at the iridium-indium-bridged phosphorus atom. A crossover experiment confirms that the conversion of 1 to 2 is intramolecular. Plausible reaction pathways for the formation of 2 and 3 are proposed.

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