Amine-induced coupling of carbonyl and nitrile ligands in tungsten (II) complexes

Journal Article · Thu Mar 31 23:00:00 EST 1994 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00016a026· OSTI ID:7019647

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

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

Reaction of [Tp[prime](CO)[sub 3] W(N[triple bond]CMe)][BF[sub 4]] (1), an intermediate formed in situ from Tp[prime]W-(CO)[sub 3]I and AgBF[sub 4] in acetonitrile, with ammonia or n-butylamine generates neutral complexes of the type Tp[prime](CO)[sub 2] [ovr W-C(=O)-N(R)-C(Me)=N](H) (R = H (2), n-butyl (3)). Protonation of these heteroatom metallacycle complexes occurs at the acyl oxygen atom to produce cationic metallacycle hydroxycarbene complexes, [Tp[prime](CO)[sub 2][ovr W=C(OH)-N(R)-C(Me)=N](H)][BF[sub 4]] (R = H (4), n-butyl (5)). NMR spectra and a single crystal X-ray structure indicate that the five-membered ring is planar and effectively lies in the molecular mirror plane with the carbene carbon adjacent to the two terminal carbonyl ligands. Methylation of the metallacycle acyl complexes at the acyl oxygen produces analogous cationic metallacycle methoxycarbene complexes of the type [Tp[prime](CO)[sub 2][ovr W=C(OMe)-N(R)-C(Me)=N](H)][CF[sub 3]SO[sub 3 ]] (R = H (6), n-butyl (7)). Reaction of the [Tp[prime](CO)[sub 3]W(N[triple bond]CMe)][BF[sub 4]] intermediate with the bulky tert-butylamine nucleophile results in formation of an unusual amido complex, Tp[prime](CO)[sub 2]W-[ovr N-C(=CH[sub 2])-N-(Bu[sup t])-C](=O) (8). 29 refs., 2 figs., 7 tabs.

• OSTI ID: 7019647
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 13:4; ISSN 0276-7333; ISSN ORGND7
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
ACETONITRILE
ALKYL RADICALS
AMIDES
AMINES
AMMONIA
BUTYL RADICALS
CARBONYLS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPILED DATA
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
HYDRIDES
HYDROGEN COMPOUNDS
HYDROGENATION
INFORMATION
INFRARED SPECTRA
KINETICS
LIGANDS
METHYLATION
MOLECULAR STRUCTURE
NITRILES
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NMR SPECTRA
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RADICALS
REACTION KINETICS
SCATTERING
SPECTRA
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
X-RAY DIFFRACTION