Alkyl nitrite complexes of ruthenium prepared by acid-base chemistry at the bound nitrosyl group

Jerry L. Walsh, R Morris Bullock, Thomas J. Meyer

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Abstract

The alkyl nitrite complexes [Ru(bpy)2(py)N(O)OR]2+ (bpy = 2,2′-bipyridine; py = pyridine; R = methyl, ethyl, n-butyl, isopropyl) have been prepared by reactions involving attack of the corresponding alkoxide ions on the nitrosyl nitrogen in [Ru(bpy)2(py)NO]3+. In the products the alkyl nitrite groups appear to be N bound. From the properties of the complexes, it seems that dπ(RuII) → π*(N(O)OR) back-bonding is significant and that the alkyl nitrite group is a better π-electron acceptor than the nitro, pyridyl, or acetonitrile groups when bound to Ru(II). The complexes form in dry acetonitrile when both alcohol and base (collidine) are added, Ru(bpy)2(py)NO3+ + ROH + B → Ru(bpy)2(py)N(O)OR2+ + BH+, and the reversible nature of the chemistry is seen following the addition of excess acid, Ru(bpy)2(py)N(O)OR2+ + H+ → Ru(bpy)2(py)NO3+ + ROH. Once formed, the alkyl nitrite complexes undergo an irreversible, one-electron oxidation (at ∼+1.75 V vs. SSCE) and the major products are [Ru(bpy)2(py)NO]3+ and ROH. The chloro analogues [Ru(bpy)2(Cl)N(O)OR]+ (R = ethyl, isopropyl) have also been prepared, in this case by attack of RO- on [Ru(bpy)2(Cl)NO]2+. It has proven difficult to characterize the complexes fully, but they appear to have properties similar to those found for the pyridyl complexes.

Original languageEnglish
Pages (from-to)865-869
Number of pages5
JournalInorganic Chemistry
Volume19
Issue number4
Publication statusPublished - 1980

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Ruthenium
nitrites
Nitrites
ruthenium
chemistry
acids
Acids
attack
acetonitrile
alkoxides
products
pyridines
alcohols
electrons
analogs
nitrogen
oxidation
bis(bipyridyl)ruthenium(II)
Electrons
ions

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Alkyl nitrite complexes of ruthenium prepared by acid-base chemistry at the bound nitrosyl group. / Walsh, Jerry L.; Bullock, R Morris; Meyer, Thomas J.

In: Inorganic Chemistry, Vol. 19, No. 4, 1980, p. 865-869.

Research output: Contribution to journalArticle

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abstract = "The alkyl nitrite complexes [Ru(bpy)2(py)N(O)OR]2+ (bpy = 2,2′-bipyridine; py = pyridine; R = methyl, ethyl, n-butyl, isopropyl) have been prepared by reactions involving attack of the corresponding alkoxide ions on the nitrosyl nitrogen in [Ru(bpy)2(py)NO]3+. In the products the alkyl nitrite groups appear to be N bound. From the properties of the complexes, it seems that dπ(RuII) → π*(N(O)OR) back-bonding is significant and that the alkyl nitrite group is a better π-electron acceptor than the nitro, pyridyl, or acetonitrile groups when bound to Ru(II). The complexes form in dry acetonitrile when both alcohol and base (collidine) are added, Ru(bpy)2(py)NO3+ + ROH + B → Ru(bpy)2(py)N(O)OR2+ + BH+, and the reversible nature of the chemistry is seen following the addition of excess acid, Ru(bpy)2(py)N(O)OR2+ + H+ → Ru(bpy)2(py)NO3+ + ROH. Once formed, the alkyl nitrite complexes undergo an irreversible, one-electron oxidation (at ∼+1.75 V vs. SSCE) and the major products are [Ru(bpy)2(py)NO]3+ and ROH. The chloro analogues [Ru(bpy)2(Cl)N(O)OR]+ (R = ethyl, isopropyl) have also been prepared, in this case by attack of RO- on [Ru(bpy)2(Cl)NO]2+. It has proven difficult to characterize the complexes fully, but they appear to have properties similar to those found for the pyridyl complexes.",
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N2 - The alkyl nitrite complexes [Ru(bpy)2(py)N(O)OR]2+ (bpy = 2,2′-bipyridine; py = pyridine; R = methyl, ethyl, n-butyl, isopropyl) have been prepared by reactions involving attack of the corresponding alkoxide ions on the nitrosyl nitrogen in [Ru(bpy)2(py)NO]3+. In the products the alkyl nitrite groups appear to be N bound. From the properties of the complexes, it seems that dπ(RuII) → π*(N(O)OR) back-bonding is significant and that the alkyl nitrite group is a better π-electron acceptor than the nitro, pyridyl, or acetonitrile groups when bound to Ru(II). The complexes form in dry acetonitrile when both alcohol and base (collidine) are added, Ru(bpy)2(py)NO3+ + ROH + B → Ru(bpy)2(py)N(O)OR2+ + BH+, and the reversible nature of the chemistry is seen following the addition of excess acid, Ru(bpy)2(py)N(O)OR2+ + H+ → Ru(bpy)2(py)NO3+ + ROH. Once formed, the alkyl nitrite complexes undergo an irreversible, one-electron oxidation (at ∼+1.75 V vs. SSCE) and the major products are [Ru(bpy)2(py)NO]3+ and ROH. The chloro analogues [Ru(bpy)2(Cl)N(O)OR]+ (R = ethyl, isopropyl) have also been prepared, in this case by attack of RO- on [Ru(bpy)2(Cl)NO]2+. It has proven difficult to characterize the complexes fully, but they appear to have properties similar to those found for the pyridyl complexes.

AB - The alkyl nitrite complexes [Ru(bpy)2(py)N(O)OR]2+ (bpy = 2,2′-bipyridine; py = pyridine; R = methyl, ethyl, n-butyl, isopropyl) have been prepared by reactions involving attack of the corresponding alkoxide ions on the nitrosyl nitrogen in [Ru(bpy)2(py)NO]3+. In the products the alkyl nitrite groups appear to be N bound. From the properties of the complexes, it seems that dπ(RuII) → π*(N(O)OR) back-bonding is significant and that the alkyl nitrite group is a better π-electron acceptor than the nitro, pyridyl, or acetonitrile groups when bound to Ru(II). The complexes form in dry acetonitrile when both alcohol and base (collidine) are added, Ru(bpy)2(py)NO3+ + ROH + B → Ru(bpy)2(py)N(O)OR2+ + BH+, and the reversible nature of the chemistry is seen following the addition of excess acid, Ru(bpy)2(py)N(O)OR2+ + H+ → Ru(bpy)2(py)NO3+ + ROH. Once formed, the alkyl nitrite complexes undergo an irreversible, one-electron oxidation (at ∼+1.75 V vs. SSCE) and the major products are [Ru(bpy)2(py)NO]3+ and ROH. The chloro analogues [Ru(bpy)2(Cl)N(O)OR]+ (R = ethyl, isopropyl) have also been prepared, in this case by attack of RO- on [Ru(bpy)2(Cl)NO]2+. It has proven difficult to characterize the complexes fully, but they appear to have properties similar to those found for the pyridyl complexes.

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