Preparation of the triiron phosphinidene-imido clusters Fe[sub 3]([mu][sub 3]-PBu[sup t])([mu][sub 3]-NR)(CO)[sub 9] (R = Et, Ph) and their reactions with alkynes

Journal Article · Wed Apr 15 00:00:00 EDT 1992 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00034a035· OSTI ID:6915526

Song, Jeongsup; Geoffroy, G L ^[1]; Rheingold, A L ^[2]

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1. Pennsylvania State Univ., University Park (United States)
2. Univ. of Delaware, Newark (United States)

The compounds Fe[sub 3]([mu][sub 3]-PBu[sup t])([mu][sub 3]-NR)(CO)[sub 9] (R = Ph (2a), Et (2b)), which are the first examples of clusters possessing both capping imido and phosphinidene ligands, have been prepared in good yield by the photochemical reaction of the corresponding H[sub 2]Fe[sub 3]([mu][sub 3]-NR)(CO)[sub 9] cluster with Bu[sup t]PCl[sub 2]. Cluster 2a has been crystallographically characterized: C[sub 19]H[sub 14]NO[sub 9]PFe[sub 3], orthorhombic,. Like Fe[sub 3]([mu][sub 3]-NPh)[sub 2](CO)[sub 9], the cluster consists of an isosceles triangle of iron atoms with two Fe-Fe bonds and with capping phosphinidene and imido ligands above and below the metal triangle. Both clusters have been observed to react with alkynes to give a variety of products, the most interesting of which is the binuclear compound Fe[sub 2]([mu][sub 2],[eta][sup 3]-PhNC(Ph) [double bond] C(Ph)PBu[sup t])([mu][sub 2],[eta][sup 4]PhC [double bond] C(Ph)C(Ph) [double bond] CPh)(CO)[sub 4] (3) which results from the reaction of PhC [triple bond] C(Ph)PBu[sup t] ligand formed by insertion of the alkyne between the phosphinidene and imido ligands and also has a ferracyclopentadiene ligand formed by coupling of two additional alkynes: C[sub 56]H[sub 44]NO[sub 4]PFe[sub 2], triclinic.

• OSTI ID: 6915526
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 31:8; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ALKYNES
BOND ANGLE
BOND LENGTHS
CARBONYLS
CHEMICAL ANALYSIS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DIFFRACTION
DIMENSIONS
HYDROCARBONS
IRON COMPLEXES
KINETICS
LENGTH
LIGANDS
MOLECULAR STRUCTURE
NMR SPECTRA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
ORTHORHOMBIC LATTICES
PHOTOCHEMICAL REACTIONS
QUALITATIVE CHEMICAL ANALYSIS
REACTION KINETICS
SCATTERING
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRICLINIC LATTICES
X-RAY DIFFRACTION