Snapshots of an alkylidyne for nitride triple-bond metathesis

被引：49

作者：

Bailey, Brad C.

Fout, Alison R.

Fan, Hongjun

Tomaszewski, John

Huffman, John C.

Gary, J. Brannon

Johnson, Marc J. A.

Mindiola, Daniel J. ^{[1
]}

机构：

[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA

[2] Indiana Univ, Ctr Mol Struct, Bloomington, IN 47405 USA

[3] Univ Michigan, Dept Chem, Ann Arbor, MI 48109 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2007年 / 129卷 / 08期

关键词：

D O I：

10.1021/ja0689684

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The transient titanium alkylidyne complex (PNP)(TiCBu)-Bu-t (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((NCRCBu)-Bu-t) (R = Bu-t, 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 (RCCBu)-Bu-t (R = Bu-t, 1; R = Ad, 2) and form neutral or zwitterionic titanium imide species, respectively. Imide formation for the latter species results from complete (BuC3-)-Bu-t for N3- metathetical exchange. Isotopic labeling studies applying N-15 enriched nitrile NCAd clearly reveal the nitrogen atom transfer results from incomplete and complete metathesis of a titanium alkylidyne with a nitrile.

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页码：2234 / +

页数：3

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