Snapshots of an alkylidyne for nitride triple-bond metathesis

Brad C. Bailey; Alison R. Fout; Hongjun Fan; John Tomaszewski; John C. Huffman; J. Brannon Gary; Marc J.A. Johnson; Daniel J. Mindiola

doi:10.1021/ja0689684

Snapshots of an alkylidyne for nitride triple-bond metathesis

Brad C. Bailey
, Alison R. Fout
, Hongjun Fan
, John Tomaszewski
, John C. Huffman
, J. Brannon Gary
, Marc J.A. Johnson
, Daniel J. Mindiola

Department of Pathology and Anatomical Sciences

Indiana University Bloomington
University of Michigan, Ann Arbor

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

54 Scopus citations

Abstract

The transient titanium alkylidyne complex (PNP)Ti≡ C^tBu (PNP = N[2-P(CHMe₂)₂-4-methylphenyl]₂^-), [2+2] cycloadds sterically bulky nitriles such as NCR to afford unique examples of kinetically stable azametallacyclobutadienes, (PNP)Ti(NCRC^tBu) (R = ^tBu, 1; Ad, 2). Complexes 1 and 2 can further react with electrophiles such as ClSi(CH₃)₃ or Al(CH₃)₃ to extrude the alkyne RC≡ C^tBu (R = ^tBu, 1; R = Ad, 2) and form neutral or zwitterionic titanium imide species, respectively. Imide formation for the latter species results from complete ^tBuC^3- for N^3- metathetical exchange. Isotopic labeling studies applying ¹⁵N enriched nitrile N≡CAd clearly reveal the nitrogen atom transfer results from incomplete and complete metathesis of a titanium alkylidyne with a nitrile.

Original language	English
Pages (from-to)	2234-2235
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	129
Issue number	8
DOIs	https://doi.org/10.1021/ja0689684
State	Published - Feb 28 2007

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@article{dfc11f3e549346799bc34a22b8349361,

title = "Snapshots of an alkylidyne for nitride triple-bond metathesis",

abstract = "The transient titanium alkylidyne complex (PNP)Ti≡ CtBu (PNP = N[2-P(CHMe2)2-4-methylphenyl]2-), [2+2] cycloadds sterically bulky nitriles such as NCR to afford unique examples of kinetically stable azametallacyclobutadienes, (PNP)Ti(NCRCtBu) (R = tBu, 1; Ad, 2). Complexes 1 and 2 can further react with electrophiles such as ClSi(CH3)3 or Al(CH3)3 to extrude the alkyne RC≡ CtBu (R = tBu, 1; R = Ad, 2) and form neutral or zwitterionic titanium imide species, respectively. Imide formation for the latter species results from complete tBuC3- for N3- metathetical exchange. Isotopic labeling studies applying 15N enriched nitrile N≡CAd clearly reveal the nitrogen atom transfer results from incomplete and complete metathesis of a titanium alkylidyne with a nitrile.",

author = "Bailey, \{Brad C.\} and Fout, \{Alison R.\} and Hongjun Fan and John Tomaszewski and Huffman, \{John C.\} and Gary, \{J. Brannon\} and Johnson, \{Marc J.A.\} and Mindiola, \{Daniel J.\}",

year = "2007",

month = feb,

day = "28",

doi = "10.1021/ja0689684",

language = "English",

volume = "129",

pages = "2234--2235",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Snapshots of an alkylidyne for nitride triple-bond metathesis

AU - Bailey, Brad C.

AU - Fout, Alison R.

AU - Fan, Hongjun

AU - Tomaszewski, John

AU - Huffman, John C.

AU - Gary, J. Brannon

AU - Johnson, Marc J.A.

AU - Mindiola, Daniel J.

PY - 2007/2/28

Y1 - 2007/2/28

N2 - The transient titanium alkylidyne complex (PNP)Ti≡ CtBu (PNP = N[2-P(CHMe2)2-4-methylphenyl]2-), [2+2] cycloadds sterically bulky nitriles such as NCR to afford unique examples of kinetically stable azametallacyclobutadienes, (PNP)Ti(NCRCtBu) (R = tBu, 1; Ad, 2). Complexes 1 and 2 can further react with electrophiles such as ClSi(CH3)3 or Al(CH3)3 to extrude the alkyne RC≡ CtBu (R = tBu, 1; R = Ad, 2) and form neutral or zwitterionic titanium imide species, respectively. Imide formation for the latter species results from complete tBuC3- for N3- metathetical exchange. Isotopic labeling studies applying 15N enriched nitrile N≡CAd clearly reveal the nitrogen atom transfer results from incomplete and complete metathesis of a titanium alkylidyne with a nitrile.

AB - The transient titanium alkylidyne complex (PNP)Ti≡ CtBu (PNP = N[2-P(CHMe2)2-4-methylphenyl]2-), [2+2] cycloadds sterically bulky nitriles such as NCR to afford unique examples of kinetically stable azametallacyclobutadienes, (PNP)Ti(NCRCtBu) (R = tBu, 1; Ad, 2). Complexes 1 and 2 can further react with electrophiles such as ClSi(CH3)3 or Al(CH3)3 to extrude the alkyne RC≡ CtBu (R = tBu, 1; R = Ad, 2) and form neutral or zwitterionic titanium imide species, respectively. Imide formation for the latter species results from complete tBuC3- for N3- metathetical exchange. Isotopic labeling studies applying 15N enriched nitrile N≡CAd clearly reveal the nitrogen atom transfer results from incomplete and complete metathesis of a titanium alkylidyne with a nitrile.

UR - https://www.scopus.com/pages/publications/33847691467

U2 - 10.1021/ja0689684

DO - 10.1021/ja0689684

M3 - Article

AN - SCOPUS:33847691467

SN - 0002-7863

VL - 129

SP - 2234

EP - 2235

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 8

ER -

Snapshots of an alkylidyne for nitride triple-bond metathesis

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