Conversion of nitriles to nitrenes via azavinylidenes in low-valent tungsten carbonyl complexes

Journal Article · Wed Sep 21 04:00:00 EDT 1994 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00098a022· OSTI ID:6840930

Feng, S G; White, P S; Templeton, J L ^[1]

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1. Univ. of North Carolina, Chapel Hill, NC (United States)

Azavinylidene complexes of the type Tp[prime](CO)[sub 2]W=N=CRNu are available from the reaction of [Tp[prime](CO)[sub 3]W(N=CR)][BF[sub 4]] with nucleophiles (Tp[prime] = hydridotris(3,5-dimethylpyrazolyl)borate; R = Me, Nu = H (1a); R = Ph, Nu = Et (1d); R = Me, Nu = MeO (1e)). Related azavinylidene complexes Tp[prime](CO)[sub 2]W=N=CHR (R = Me (1a); R = Et (1b); R = CH[sub 2]Ph (1c)) form via insertion of nitrile into the W-H bond of Tp[prime](CO)[sub 3]WH when the metal reagent is photolyzed in the presence of nitriles. Donation of the lone pair of electrons from the azavinylidene nitrogen to the tungsten center, compatible with electron counting guidelines, is reflected in the low IR stretching frequencies of the carbonyl ligands and their downfield carbon resonance in [sup 15]C NMR. NMR spectra and an X-ray structure of Tp[prime](CO)[sub 2]W=N=CHCH[sub 3]Ph (1c) indicate that the azavinylidene ligand is nearly linear ([sup 3]J[sub WH] = 5.6 Hz, [sup 2]J[sub WC] = 27 Hz, and [alpha](W-N-C) = 166.6(7)[degree]). Complex 1c crystallized in the monoclinic space group P2[sub 1]/n with unit cell dimensions of a = 12.163(1), b = 17.207(2), and c = 13.312(1) [angstrom] and [beta] = 102.103(7)[degree], with Z = 4. 32 refs., 2 figs., 5 tabs.

• OSTI ID: 6840930
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 116:19; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPILED DATA
COMPLEXES
CRYSTAL STRUCTURE
DATA
DECOMPOSITION
DIFFRACTION
INFORMATION
LIGANDS
MAGNETIC RESONANCE
NITRILES
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RESONANCE
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
X-RAY DIFFRACTION