The Quest for Double Vicinal C-H Bond Activation on the (eta(5):eta(5)-Fulvalene)diiridium Platform: Syntheses and Structures of (eta(5):eta(5)-Fulvalene)Ir-2(ortho-mu-C6H4)(CO)(2)(Ir-Ir) and Related Complexes

Judith Baumgartner, Robert G. Bergmann, Berndt Kayser, Theodore P. Klupinski, Yong Kwang Park, K. Peter C. Vollhardt, Michael J. West, Bolin Zhu

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The fulvalene diiridium platform was scrutinized for its potential to effect double vicinal C-H activation of C 6 H 6 and C 6 H 12 , respectively. For this purpose, an improved preparation of Fv[Ir(CO) 2 ] 2 was developed, and the syntheses of the new complexes FvIr(CO) 2 Ir(CO)(η 2 -C 6 F 6 ), Fv[Ir(CO)(η 2 -C 6 F 6 )] 2 , Fv[Ir(CH 2 =CH 2 ) 2 ] 2 (X-ray), Fv[Ir(PMe 3 )(H) 2 ] 2 (X-ray), and (2,2′,3,3′-tetra- tert -butylFv)[Ir(CO) 2 ] 2 were accomplished. When irradiated in C 6 H 6 , these molecules succeeded to varying degrees, and best for (2,2′,3,3′-tetra- tert -butylFv)[Ir(CO) 2 ] 2 , in the double metalation of the aromatic ring to engender ligating Ir 2 (ortho - μ -C 6 H 4 )(CO) 2 (Ir - Ir) moieties, in addition to their precursor mono(phenyliridium hydride) constructs. A competing photochemical pathway is evident by the formation of diastereomers of Fv (or 2,2',3,3'-tetra- tert -butylFv) [Ir(CO)(Ph)(H)] 2 and the resulting dehydrogenated ligated [Ir(CO)(Ph)] 2 (Ir - Ir). The structures of FvIr 2 (ortho - μ -C 6 H 4 )(CO) 2 (Ir - Ir) and trans -Fv[Ir(CO)(Ph)] 2 (Ir - Ir) were corroborated by X-ray analyses. Efforts to realize C-H bond activations with C 6 H 12 generally failed or fared very poorly, with the exception of the tert -butylFv system, which enabled single, but not further, insertion to give (2,2′,3,3′-tetra- tert -butylFv)[Ir(CO)(Cy)(H)][Ir(CO) 2 ] in 34% yield. To explore the relevant chemistry of phenyl- and alkyliridium species attached to Fv, several such derivatives were made by independent routes, adding knowledge to the fundamental behavior of this category of molecules. Where appropriate and for comparative purposes, similar reactions were performed on the corresponding Cp- and 1,2-di- tert -butylCpIr(CO) 2 relatives.

Original languageEnglish
Pages (from-to)2409-2429
Number of pages21
JournalSynthesis
Volume51
Issue number11
DOIs
Publication statusPublished - 2019

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Carbon Monoxide
Chemical activation
X rays
Molecules
Hydrides
Derivatives

Keywords

  • benzyne
  • C-H activation
  • dinuclear complexes
  • iridium
  • photochemistry

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

Cite this

The Quest for Double Vicinal C-H Bond Activation on the (eta(5):eta(5)-Fulvalene)diiridium Platform: Syntheses and Structures of (eta(5):eta(5)-Fulvalene)Ir-2(ortho-mu-C6H4)(CO)(2)(Ir-Ir) and Related Complexes. / Baumgartner, Judith; Bergmann, Robert G. ; Kayser, Berndt; Klupinski, Theodore P.; Park, Yong Kwang; Vollhardt, K. Peter C. ; West, Michael J.; Zhu, Bolin.

In: Synthesis, Vol. 51, No. 11, 2019, p. 2409-2429.

Research output: Contribution to journalArticleResearchpeer-review

Baumgartner, Judith ; Bergmann, Robert G. ; Kayser, Berndt ; Klupinski, Theodore P. ; Park, Yong Kwang ; Vollhardt, K. Peter C. ; West, Michael J. ; Zhu, Bolin. / The Quest for Double Vicinal C-H Bond Activation on the (eta(5):eta(5)-Fulvalene)diiridium Platform: Syntheses and Structures of (eta(5):eta(5)-Fulvalene)Ir-2(ortho-mu-C6H4)(CO)(2)(Ir-Ir) and Related Complexes. In: Synthesis. 2019 ; Vol. 51, No. 11. pp. 2409-2429.
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title = "The Quest for Double Vicinal C-H Bond Activation on the (eta(5):eta(5)-Fulvalene)diiridium Platform: Syntheses and Structures of (eta(5):eta(5)-Fulvalene)Ir-2(ortho-mu-C6H4)(CO)(2)(Ir-Ir) and Related Complexes",
abstract = "The fulvalene diiridium platform was scrutinized for its potential to effect double vicinal C-H activation of C 6 H 6 and C 6 H 12 , respectively. For this purpose, an improved preparation of Fv[Ir(CO) 2 ] 2 was developed, and the syntheses of the new complexes FvIr(CO) 2 Ir(CO)(η 2 -C 6 F 6 ), Fv[Ir(CO)(η 2 -C 6 F 6 )] 2 , Fv[Ir(CH 2 =CH 2 ) 2 ] 2 (X-ray), Fv[Ir(PMe 3 )(H) 2 ] 2 (X-ray), and (2,2′,3,3′-tetra- tert -butylFv)[Ir(CO) 2 ] 2 were accomplished. When irradiated in C 6 H 6 , these molecules succeeded to varying degrees, and best for (2,2′,3,3′-tetra- tert -butylFv)[Ir(CO) 2 ] 2 , in the double metalation of the aromatic ring to engender ligating Ir 2 (ortho - μ -C 6 H 4 )(CO) 2 (Ir - Ir) moieties, in addition to their precursor mono(phenyliridium hydride) constructs. A competing photochemical pathway is evident by the formation of diastereomers of Fv (or 2,2',3,3'-tetra- tert -butylFv) [Ir(CO)(Ph)(H)] 2 and the resulting dehydrogenated ligated [Ir(CO)(Ph)] 2 (Ir - Ir). The structures of FvIr 2 (ortho - μ -C 6 H 4 )(CO) 2 (Ir - Ir) and trans -Fv[Ir(CO)(Ph)] 2 (Ir - Ir) were corroborated by X-ray analyses. Efforts to realize C-H bond activations with C 6 H 12 generally failed or fared very poorly, with the exception of the tert -butylFv system, which enabled single, but not further, insertion to give (2,2′,3,3′-tetra- tert -butylFv)[Ir(CO)(Cy)(H)][Ir(CO) 2 ] in 34{\%} yield. To explore the relevant chemistry of phenyl- and alkyliridium species attached to Fv, several such derivatives were made by independent routes, adding knowledge to the fundamental behavior of this category of molecules. Where appropriate and for comparative purposes, similar reactions were performed on the corresponding Cp- and 1,2-di- tert -butylCpIr(CO) 2 relatives.",
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T1 - The Quest for Double Vicinal C-H Bond Activation on the (eta(5):eta(5)-Fulvalene)diiridium Platform: Syntheses and Structures of (eta(5):eta(5)-Fulvalene)Ir-2(ortho-mu-C6H4)(CO)(2)(Ir-Ir) and Related Complexes

AU - Baumgartner, Judith

AU - Bergmann, Robert G.

AU - Kayser, Berndt

AU - Klupinski, Theodore P.

AU - Park, Yong Kwang

AU - Vollhardt, K. Peter C.

AU - West, Michael J.

AU - Zhu, Bolin

PY - 2019

Y1 - 2019

N2 - The fulvalene diiridium platform was scrutinized for its potential to effect double vicinal C-H activation of C 6 H 6 and C 6 H 12 , respectively. For this purpose, an improved preparation of Fv[Ir(CO) 2 ] 2 was developed, and the syntheses of the new complexes FvIr(CO) 2 Ir(CO)(η 2 -C 6 F 6 ), Fv[Ir(CO)(η 2 -C 6 F 6 )] 2 , Fv[Ir(CH 2 =CH 2 ) 2 ] 2 (X-ray), Fv[Ir(PMe 3 )(H) 2 ] 2 (X-ray), and (2,2′,3,3′-tetra- tert -butylFv)[Ir(CO) 2 ] 2 were accomplished. When irradiated in C 6 H 6 , these molecules succeeded to varying degrees, and best for (2,2′,3,3′-tetra- tert -butylFv)[Ir(CO) 2 ] 2 , in the double metalation of the aromatic ring to engender ligating Ir 2 (ortho - μ -C 6 H 4 )(CO) 2 (Ir - Ir) moieties, in addition to their precursor mono(phenyliridium hydride) constructs. A competing photochemical pathway is evident by the formation of diastereomers of Fv (or 2,2',3,3'-tetra- tert -butylFv) [Ir(CO)(Ph)(H)] 2 and the resulting dehydrogenated ligated [Ir(CO)(Ph)] 2 (Ir - Ir). The structures of FvIr 2 (ortho - μ -C 6 H 4 )(CO) 2 (Ir - Ir) and trans -Fv[Ir(CO)(Ph)] 2 (Ir - Ir) were corroborated by X-ray analyses. Efforts to realize C-H bond activations with C 6 H 12 generally failed or fared very poorly, with the exception of the tert -butylFv system, which enabled single, but not further, insertion to give (2,2′,3,3′-tetra- tert -butylFv)[Ir(CO)(Cy)(H)][Ir(CO) 2 ] in 34% yield. To explore the relevant chemistry of phenyl- and alkyliridium species attached to Fv, several such derivatives were made by independent routes, adding knowledge to the fundamental behavior of this category of molecules. Where appropriate and for comparative purposes, similar reactions were performed on the corresponding Cp- and 1,2-di- tert -butylCpIr(CO) 2 relatives.

AB - The fulvalene diiridium platform was scrutinized for its potential to effect double vicinal C-H activation of C 6 H 6 and C 6 H 12 , respectively. For this purpose, an improved preparation of Fv[Ir(CO) 2 ] 2 was developed, and the syntheses of the new complexes FvIr(CO) 2 Ir(CO)(η 2 -C 6 F 6 ), Fv[Ir(CO)(η 2 -C 6 F 6 )] 2 , Fv[Ir(CH 2 =CH 2 ) 2 ] 2 (X-ray), Fv[Ir(PMe 3 )(H) 2 ] 2 (X-ray), and (2,2′,3,3′-tetra- tert -butylFv)[Ir(CO) 2 ] 2 were accomplished. When irradiated in C 6 H 6 , these molecules succeeded to varying degrees, and best for (2,2′,3,3′-tetra- tert -butylFv)[Ir(CO) 2 ] 2 , in the double metalation of the aromatic ring to engender ligating Ir 2 (ortho - μ -C 6 H 4 )(CO) 2 (Ir - Ir) moieties, in addition to their precursor mono(phenyliridium hydride) constructs. A competing photochemical pathway is evident by the formation of diastereomers of Fv (or 2,2',3,3'-tetra- tert -butylFv) [Ir(CO)(Ph)(H)] 2 and the resulting dehydrogenated ligated [Ir(CO)(Ph)] 2 (Ir - Ir). The structures of FvIr 2 (ortho - μ -C 6 H 4 )(CO) 2 (Ir - Ir) and trans -Fv[Ir(CO)(Ph)] 2 (Ir - Ir) were corroborated by X-ray analyses. Efforts to realize C-H bond activations with C 6 H 12 generally failed or fared very poorly, with the exception of the tert -butylFv system, which enabled single, but not further, insertion to give (2,2′,3,3′-tetra- tert -butylFv)[Ir(CO)(Cy)(H)][Ir(CO) 2 ] in 34% yield. To explore the relevant chemistry of phenyl- and alkyliridium species attached to Fv, several such derivatives were made by independent routes, adding knowledge to the fundamental behavior of this category of molecules. Where appropriate and for comparative purposes, similar reactions were performed on the corresponding Cp- and 1,2-di- tert -butylCpIr(CO) 2 relatives.

KW - benzyne

KW - C-H activation

KW - dinuclear complexes

KW - iridium

KW - photochemistry

UR - http://www.scopus.com/inward/record.url?scp=85065880786&partnerID=8YFLogxK

U2 - 10.1055/s-0037-1611736

DO - 10.1055/s-0037-1611736

M3 - Article

VL - 51

SP - 2409

EP - 2429

JO - Synthesis

JF - Synthesis

SN - 0039-7881

IS - 11

ER -