Reactions of isocyanide-substituted dimanganese carbonyl complexes with alkynes. Alkyne-isocyanide coupling and the synthesis of metalated n-substituted pyridines

Journal Article · Sun Jan 01 04:00:00 EST 1995 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00001a069· OSTI ID:6602733

Adams, R D; Huang, M ^[1]

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1. Univ. of South Carolina, Columbia, SC (United States)

When activated by Me[sub 3]NO in the presence of MeCN, the compounds Mn[sub 2](CO)[sub 9](CNR) (la,b; R = Me, Ph) react with MeO[sub 2]O[sub 2]CC[triple bond]CCO[sub 2]Me to yield the new compounds Mn[sub 2](CO)[sub 8][[mu]-(MeO[sub 2]C)C=C(CO[sub 2]Me)C=NR] (2a,b; R = Me, Ph) in yields of 40% and 32%, respectively. Minor products, Mn[sub 2](CO)[sub 7](CNR)[[mu]-(MeO[sub 2]C)C=C(CO[sub 2]Me)-C=O] (3a,b; R = Me, Ph) were also formed. Compound 2a was characterized crystallographically. The structure shows that the isocyanide ligand was coupled to the alkyne, and the nitrogen atom is coordinated to one of the manganese atoms to form a five-membered cyclo-mangana enimine ring. One of the carboxylate groups is coordinated to the other manganese atom. The compounds (4a), (4b), and (4c) were prepared in yields of 27%, 32%, and 31%, respectively, by treatment of 2a,b with C[sub 2]H[sub 2], and of 2a with HC[sub 2](CO[sub 2]Me) in the presence of UV irradiation. Compound 4a was characterized crystallographically. This compound contains a metalated N-methylpyridine ring formed by a 1,4-cycloaddition of the alkyne to the enimine grouping in compound 2a. One of the metal atoms was shifted to a n-bonding coordination involving four of the carbon atoms of the pyridine ring. 14 refs., 2 figs., 7 tabs.

• OSTI ID: 6602733
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 14:1; ISSN 0276-7333; ISSN ORGND7
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400101 -- Activation
Nuclear Reaction
Radiometric & Radiochemical Procedures
400201* -- Chemical & Physicochemical Properties
ALKYNES
AZINES
BOND ANGLE
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
COUPLING
CRYSTALLOGRAPHY
CYANIDES
DATA
DIFFRACTION
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
INFORMATION
MANGANESE COMPLEXES
MANGANESE COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PYRIDINES
SCATTERING
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION