NO bond length/stretching frequency realtionships in C-nitroso compounds and their coordination complexes

M. Cameron, B. G. Gowenlock, G. Vasapollo

Research output: Contribution to journalArticle

Abstract

The mode of coordination of monomeric C-nitroso compounds to metals is discussed. In contrast to previous studies it is proposed that an understanding of the v(NO)/r(NO) and r(CN)/r(NO) relationships in the non-coordinated nitrosocompounds is of primary importance for assesment of the coordination mode. It is concluded that both v(NO)/R(NO) and r(CN)/r(NO) have linear interrelationships in C-nitroso compounds that the coordination compounds of RNO have the same v(NO)/r(NO) relationship as the non-coordinated monomers. Previous correlations of ?v(NO) with coordination mode are therefore correlations of r(NO) with coordination mode. s-N and s-O complexes of aromatic RNO conform to the same R(CN)/r(NO) equation (within a very small error) as the non-coordinated monomers. The extent of deviation from the r(CN)/(r(NO) relationship for complexes of aliphatic RNO is of a similar order of magnitude to that which occurs when C-nitroso monomers form the trans-dimer. The coordination mode of aliphatic RNO is, with one exception, s-N. Nitrosobenzene has a variety of coordination modes to transition metals but does not display s-O coordination. p-Nitrosodimethylaniline undergoes s-O coordination to d10 metals. © 1991.

Original languageEnglish
Pages (from-to)325-333
Number of pages9
JournalJournal of Organometallic Chemistry
Volume403
Issue number3
Publication statusPublished - 19 Feb 1991

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Nitroso Compounds
Coordination Complexes
Bond length
Stretching
Monomers
Metals
Dimers
Transition metals

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abstract = "The mode of coordination of monomeric C-nitroso compounds to metals is discussed. In contrast to previous studies it is proposed that an understanding of the v(NO)/r(NO) and r(CN)/r(NO) relationships in the non-coordinated nitrosocompounds is of primary importance for assesment of the coordination mode. It is concluded that both v(NO)/R(NO) and r(CN)/r(NO) have linear interrelationships in C-nitroso compounds that the coordination compounds of RNO have the same v(NO)/r(NO) relationship as the non-coordinated monomers. Previous correlations of ?v(NO) with coordination mode are therefore correlations of r(NO) with coordination mode. s-N and s-O complexes of aromatic RNO conform to the same R(CN)/r(NO) equation (within a very small error) as the non-coordinated monomers. The extent of deviation from the r(CN)/(r(NO) relationship for complexes of aliphatic RNO is of a similar order of magnitude to that which occurs when C-nitroso monomers form the trans-dimer. The coordination mode of aliphatic RNO is, with one exception, s-N. Nitrosobenzene has a variety of coordination modes to transition metals but does not display s-O coordination. p-Nitrosodimethylaniline undergoes s-O coordination to d10 metals. {\circledC} 1991.",
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NO bond length/stretching frequency realtionships in C-nitroso compounds and their coordination complexes. / Cameron, M.; Gowenlock, B. G.; Vasapollo, G.

In: Journal of Organometallic Chemistry, Vol. 403, No. 3, 19.02.1991, p. 325-333.

Research output: Contribution to journalArticle

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