Isocyanide insertion reactions and their role in the cluster-catalyzed hydrogenation of isocyanide molecules

Journal Article · Wed May 09 04:00:00 EDT 1979 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00504a013· OSTI ID:6063460

Adams, R D; Golembeski, N M

Studies of the reactions of H/sub 2/Os/sub 3/(CO)/sub 10/ with the isocyanide molecules, CNR, R = C/sub 6/H/sub 5/, CH/sub 3/, t-C/sub 4/H/sub 9/, are reported. The initial products are 1 : 1 adducts of the type H(..mu..-H)Os/sub 3/(CO)/sub 10/CNR. A hydrogen atom can be transferred to the isocyanide ligand in two different ways depending on the reaction conditions. In strong donor solvents compounds of the type (..mu..-H)(..mu..-C==N(H)R)Os/sub 3/(CO)/sub 10/ are obtained apparently through a proton dissociation and readdition process. When heated in weak donor solvents a hydrogen atom is transferred to the carbon atom. This evidently occurs through an intramolecular insertion type process. The initial products, (..mu..-H)(..mu..-eta/sup 2/-HC==NR)Os/sub 3/(CO)/sub 10/, R = C/sub 6/H/sub 5/, CH/sub 3/, contain a formimidoyl ligand bridging the edge of the cluster. With further heating these compounds lose CO, reversibly, to form the complexes (..mu..-H)(..mu../sub 3/-eta/sup 2/-HC==NR)Os/sub 3/(CO)/sub 9/, R = C/sub 6/H/sub 5/, CH/sub 3/, in which the formimidoyl ligand is bonded to the face of the cluster. An x-ray crystallographic analysis of the compound (..mu..-H)(..mu../sub 3/-eta/sup 2/-HC==NC/sub 6/H/sub 5/)Os/sub 3/(CO)/sub 9/ is reported. This compound reacts with P(OCH/sub 3/)/sub 3/ to form the adduct (..mu..-H)(..mu..-eta/sup 2/-HC==NC/sub 6/H/sub 5/)Os/sub 3/(CO)/sub 9/(P(OCH/sub 3/)/sub 3/) which contains an edge-bridging formimidoyl ligand. An x-ray crystallographic analysis of this compound is also reported. From the reaction solutions which have produced the formimidoyl-containing products, the compounds (..mu..-H)/sub 2/Os/sub 3/(CO)/sub 9/(CNR), R = C/sub 6/H/sub 5/, CH/sub 3/, t-C/sub 4/H/sub 9/, have been isolated. The possible role of these compounds in the formation of the formimidoyl-containing products is discussed. 4 figures, 9 tables.

• Research Organization: Yale Univ., New Haven, CT
• OSTI ID: 6063460
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:10; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ADDUCTS
AMINES
BOND ANGLE
CARBONYLS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHLORINATED ALIPHATIC HYDROCARBONS
CHLOROFORM
COHERENT SCATTERING
COMPARATIVE EVALUATIONS
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA FORMS
DIFFRACTION
DISTANCE
ELEMENTS
EXPERIMENTAL DATA
FURANS
HALOGENATED ALIPHATIC HYDROCARBONS
HETEROCYCLIC COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
INFRARED SPECTRA
INTERATOMIC DISTANCES
ISOLATED VALUES
MAGNETIC RESONANCE
METALS
MOLECULAR STRUCTURE
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OSMIUM
OSMIUM COMPLEXES
OSMIUM COMPOUNDS
PLATINUM METALS
REFRACTORY METALS
RESONANCE
SCATTERING
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
THERMAL DEGRADATION
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS
X-RAY DIFFRACTION
YIELDS