Formation and cleavage of N-H bonds on nitrido metal carbonyl clusters

Journal Article · Wed Apr 30 04:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00269a028· OSTI ID:5456579

Blohm, M L; Fjare, D E; Gladfelter, W L

A study of the protonation of three tetranuclear nitrido clusters having the butterfly geometry is reported. While the final product of each of these reactions is a hydrido-nitrido cluster, the intermediates contain the imido (NH) ligand which can be trapped by CO. For (FeRu/sub 3/N(CO)/sub 12/)/sup 1 -/, the products of protonation in a CO atmosphere are FeRu/sub 2/(NH)(CO)/sub 10/, (FeRu/sub 4/N(CO)/sub 14/)/sup 1 -/, and small amounts of HFeRu/sub 3/N(CO)/sub 12/ and Ru/sub 3/(CO)/sub 12/. With (Ru/sub 4/N(CO)/sub 12/)/sup 1 -/, this reaction generates Ru/sub 3/(NH)(CO)/sub 10/, (Ru/sub 5/N(CO)/sub 14/)/sup 1 -/, HRu/sub 4/N(CO)/sub 12/, and small quantities of Ru/sub 3/(CO)/sub 12/. The new NH-containing clusters FeRu/sub 2/(NH)(CO)/sub 10/ and Ru/sub 3/(NH)(CO)/sub 10/ contain a triply bridging N-H ligand and a triply bridging carbon monoxide. The substituted cluster (FeRu/sub 3/N(CO)/sub 10/(P(OCH/sub 3/)/sub 3/)/sub 2/)/sup 1 -/ was shown by x-ray crystallography (crystal system = orthorhombic, space group = Pnn2, a = 11.603 (3) A, b = 18.521 (6) A, c = 8.908 (4) A, Z = 2) to contain the two Ru(CO)/sub 2/(P(OCH/sub 3/)/sub 3/) fragments in the wing-tip positions. Protonation leads to a green intermediate that reacts with CO to give FeRu/sub 2/(NH)(CO)/sub 9/(P(OCH/sub 3/)/sub 3/), which was structurally characterized (crystal system = monoclinic, space group = P2/sup 1//m, a = 8.596 (2) A, b = 15.576 (3) A, c = 7.870 (4) A, ..beta.. = 100.37 (3)/sup 0/, Z = 2). The structure contains both a triply bridging CO and NH ligand, and the phosphite is bound to a ruthenium and oriented trans to the NH group. /sup 1/H and /sup 15/N NMR spectroscopies were used to identify the intermediate imido cluster feRu/sub 3/(NH)(CO)/sub 10/(P(OCH/sub 3/)/sub 3/)/sub 2/.

• Research Organization: Univ. of Minnesota, Minneapolis
• OSTI ID: 5456579
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:9; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

090310 -- Inorganic Hydrogen Compound Fuels-- Properties-- (1976-1989)
090320 -- Inorganic Hydrogen Compound Fuels-- Preparation-- (1976-1989)
10 SYNTHETIC FUELS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CATALYSTS
CHALCOGENIDES
CHEMICAL BONDS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
ELEMENTS
EXPERIMENTAL DATA
HYDROGEN
HYDROGEN COMPLEXES
INFORMATION
IRON COMPLEXES
LATTICE PARAMETERS
LIGANDS
NITROGEN
NITROGEN COMPLEXES
NMR SPECTRA
NONMETALS
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
REACTION INTERMEDIATES
RUTHENIUM COMPLEXES
SCATTERING
SPACE GROUPS
SPECTRA
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION