Reactivity of tetramethylpyrrole complexes of ruthenium and osmium

Journal Article · Sat Jan 01 04:00:00 EST 1994 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00013a016· OSTI ID:5066714

Kvietok, F; Allured, V; Carperos, V; DuBois, M R ^[1]

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1. Univ. of Colorado, Boulder, CO (United States)

Reaction of [(p-cymene)M(OTf)[sub 2]][sub x] with tetramethylpyrrole leads to the formation of [(p-cymene)M(NC[sub 4]Me[sub 4])]OTf, 1 when M = Ru, 2 when M = Os. Complex 1 crystallized in space group P2[sub 1]2[sub 1]2[sub 1] with unit cell dimensions a = 8.928(2) A, b = 13.772(4) A, c = 17.272(6) A, V = 2123.7(11) A[sup 3], and Z = 4. The crystal structure establishes that 1 is a sandwich complex with [eta][sup 6]-cymene and [eta][sup 5]-pyrrolyl ligands. Reaction of 1 or 2 with excess methyl triflate results in alkylation of the pyrrole nitrogen to form ([eta][sup 6]-p-cymene)M([eta][sup 5]-MeNC[sub 4]Me[sub 4])(OTf)[sub 2], 3 when M = Ru and 4 when M = Os. Reactions of 1 or 2 with LiAl(O-t-Bu)[sub 3]H result in nucleophilic attack of hydride on the cymene ligand to form ([eta][sup 6]-cymH)M([eta][sup 5]-NC[sub 4]Me[sub 4]), 5 when M = Ru, 6 when M = Os. Complexes 5 and 6 have been identified by one and two dimensional [sup 1]H NMR spectroscopy. Nucleophilic attack on the cymene ligand of 1 and 2 appears to be quite general, and the products of methoxide addition, ([eta][sup 5]-cymOMe)M([eta][sup 5]-NC[sub 4]Me[sub 4]) 7 when M = Ru, 8 when M = Os have also been characterized by [sup 1]H NMR data. In contrast, reactions of the pentamethylpyrrole complexes 3 and 4 with nucleophiles lead to nucleophilic addition to the pentamethylpyrrole ligand. For example, the reaction of 3 with LiAl(O-t-Bu)[sub 3]H resulted in the formation of ([eta][sup 6]-p-cymene)Ru([eta][sup 4]-MeNC[sub 4]Me[sub 4]H)OTf, 10, which was characterized by an X-ray diffraction study. 10 crystallized in space group P2[sub 1]c with a = 8.153(2) [degrees], b = 17.351 (2) [angstrom], c = 16.508(2) [angstrom], beta = 104.396(13)[degrees], V = 2261.9(7) [angstrom][sup 3], and Z = 4. 28 refs., 5 figs., 3 tabs.

• OSTI ID: 5066714
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 13:1; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
AZOLES
CHEMICAL REACTIONS
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPILED DATA
COMPLEXES
CRYSTALLOGRAPHY
DATA
DIFFRACTION
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
HYDROCHLORIC ACID
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
LIGANDS
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OSMIUM COMPLEXES
PYRROLES
RESONANCE
RUTHENIUM COMPLEXES
SCATTERING
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION