Photochemical C(sp)–C(sp2) Bond Activation in Phosphaalkynes: A New Route to Reactive Terminal Cyaphido Complexes LnM–C≡P

Görlich, Tim; Frost, Daniel S.; Boback, Nico; Coles, Nathan T.; Dittrich, Birger; Müller, Peter; Jones, William D.; Müller, Christian

doi:10.1021/jacs.1c07370

Photochemical C(sp)–C(sp²) Bond Activation in Phosphaalkynes: A New Route to Reactive Terminal Cyaphido Complexes L_nM–C≡P

Journal Article · Wed Nov 10 00:00:00 EST 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.1c07370· OSTI ID:1832447

Görlich, Tim ^[1]; Frost, Daniel S. ^[2]; Boback, Nico ^[2]; ^[2]; Dittrich, Birger ^[3]; ^[4]; ^[5]; ^[2]

Freie Univ. Berlin (Germany); University of Rochester
Freie Univ. Berlin (Germany)
Fakultät, Univ. Zürich (Switzerland)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Univ. of Rochester, NY (United States)

The photochemical activation of the C(sp)–C(sp²) bond in Pt(0)-η²-aryl-phosphaalkyne complexes leads selectively to coordination compounds of the type L_nPt(aryl)(C≡P). The oxidative addition reaction is a novel, clean, and atom-economic route for the synthesis of reactive terminal Pt(II)-cyaphido complexes, which can undergo [3 + 2] cycloaddition reactions with organic azides, yielding the corresponding Pt(II)-triazaphospholato complexes. The C–C bond cleavage reaction is thermodynamically uphill. Upon heating, the reverse and quantitative reductive elimination toward the Pt(0)-phosphaalkyne-π-complex is observed.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Rochester, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0020230

OSTI ID:: 1832447

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 46 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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CCDC 2096680: Experimental Crystal Structure Determination Tim, Görlich,; S., Frost, Daniel; Nico, Boback, https://doi.org/10.5517/ccdc.csd.cc28crv8 The current record is supplemented by this dataset	dataset	January 2021
CCDC 2096826: Experimental Crystal Structure Determination Tim, Görlich,; S., Frost, Daniel; Nico, Boback, https://doi.org/10.5517/ccdc.csd.cc28cxk4 The current record is supplemented by this dataset	dataset	January 2021
CCDC 2096827: Experimental Crystal Structure Determination Tim, Görlich,; S., Frost, Daniel; Nico, Boback, https://doi.org/10.5517/ccdc.csd.cc28cxl5 The current record is supplemented by this dataset	dataset	January 2021
CCDC 2096828: Experimental Crystal Structure Determination Tim, Görlich,; S., Frost, Daniel; Nico, Boback, https://doi.org/10.5517/ccdc.csd.cc28cxm6 The current record is supplemented by this dataset	dataset	January 2021
CCDC 2096829: Experimental Crystal Structure Determination Tim, Görlich,; S., Frost, Daniel; Nico, Boback, https://doi.org/10.5517/ccdc.csd.cc28cxn7 The current record is supplemented by this dataset	dataset	January 2021
CCDC 2096830: Experimental Crystal Structure Determination Tim, Görlich,; S., Frost, Daniel; Nico, Boback, https://doi.org/10.5517/ccdc.csd.cc28cxp8 The current record is supplemented by this dataset	dataset	January 2021

Photochemical C(sp)–C(sp2) Bond Activation in Phosphaalkynes: A New Route to Reactive Terminal Cyaphido Complexes LnM–C≡P

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Photochemical C(sp)–C(sp²) Bond Activation in Phosphaalkynes: A New Route to Reactive Terminal Cyaphido Complexes L_nM–C≡P