A distinctly bent metal-nitrosyl bond. The preparation and structure of chlorocarbonylnitrosylbis(triphenylphosphine)iridium tetrafluoroborate, [IrCl(CO)(NO)(P(C6H5)3)2][BF4]

Hodgson, Derek J.; Payne, Nicholas C.; McGinnety, J. A.; Pearson, Ralph G.; Ibers, James A.

doi:10.1021/ja01018a069

Cited by 65 publications

(25 citation statements)

References 5 publications

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“…The MNO segment should be linear for |N]O| + but bent for |N]O| − . [81,82] The snag is that the MNO angles vary, indicating fractional NO bond orders and problematic oxidation-state assignments. [83–85] Enemark and Feltham[86] avoided oxidation states in nitrosyl complexes altogether by adopting a [MNO] n notation, where n is the number of valence electrons on the metal when the ligand is formally NO + .…”

Section: Non-innocent Ligands: Nitrosylmentioning

confidence: 99%

“…We adopt the bond-valence approach:S ingle-crystal neutron diffraction of Ba[Fe(CN) 5 (NO)]·3 H 2 O [79] yields an NO bond length of 1.12 , shorter than the 1.15 [80] in NO gas.C onsidering that the 8ÀN rule for oxygen will tend to decrease the actual bond order towards two,t he observed bond length suggests j NO j + ,hence Fe 2+ .The diamagnetism of nitroprusside confirms this:T he electron configuration at Fe is low-spin d 6 and OS Fe =+2. Theoctahedral field of strong splitters keeps the low-spin configuration even upon reduction to [Fe(CN) 5 [81,82] Thes nag is that the MNO angles vary,i ndicating fractional NO bond orders and problematic oxidation-state assignments. [83][84][85] Enemark and Feltham [86] avoided oxidation states in nitrosyl complexes altogether by adopting a{ MNO} n notation, where n is the number of valence electrons on the metal when the ligand is formally NO + .…”

Section: Non-innocent Ligands:n Itrosylmentioning

confidence: 99%

“…Many nitrosyl complexes are not as straightforward. The MNO segment should be linear for |NO| + but bent for |NO| − 81. 82 The snag is that the MNO angles vary, indicating fractional NO bond orders and problematic oxidation‐state assignments 83–85.…”

Section: Non‐innocent Ligands: Nitrosylmentioning

confidence: 99%

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Oxidation State, A Long‐Standing Issue!

Karen

2015

Angew Chem Int Ed

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Section: Non-innocent Ligands: Nitrosylmentioning

confidence: 99%

Section: Non-innocent Ligands:n Itrosylmentioning

confidence: 99%

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Oxidation State, A Long‐Standing Issue!

Karen

2015

Angew Chem Int Ed

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“…As apparent from the Lewis formula, the MNO bond angle will be linear with |N≡O| + but bent for |N = O| − [166,167]. The snag is that the MNO bond angles in various NO 4 − has two tetrahedral angles and two ~160° [171].…”

Section: Nitrosyl Complexes In Generalmentioning

confidence: 99%

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Karen

McArdle

Takats

2014

Pure and Applied Chemistry

111

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A generic definition of oxidation state (OS) is formulated: "The OS of a bonded atom equals its charge after ionic approximation". In the ionic approximation, the atom that contributes more to the bonding molecular orbital (MO) becomes negative. This sign can also be estimated by comparing Allen electronegativities of the two bonded atoms, but this simplification carries an exception when the more electronegative atom is bonded as a Lewis acid. Two principal algorithms are outlined for OS determination of an atom in a compound; one based on composition, the other on topology. Both provide the same generic OS because both the ionic approximation and structural formula obey rules of stable electron configurations. A sufficiently simple empirical formula yields OS via the algorithm of direct ionic approximation (DIA) by these rules. The topological algorithm works on a Lewis formula (for a molecule) or a bond graph (for an extended solid) and has two variants. One assigns bonding electrons to more electronegative bond partners, the other sums an atom's formal charge with bond orders (or bond valences) of sign defined by the ionic approximation of each particular bond at the atom. A glossary of terms and auxiliary rules needed for determination of OS are provided, illustrated with examples, and the origins of ambiguous OS values are pointed out. An electrochemical OS is suggested with a nominal value equal to the average OS for atoms of the same element in a moiety that is charged or otherwise electrochemically relevant.

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“…Viele Nitrosylkomplexe sind nicht so unkompliziert. Das MNO‐Segment sollte für |NO| + linear sein, aber gebogen für |NO| − 81. 82 Der Haken ist, dass die MNO‐Winkel variieren und damit auf gebrochenzahlige NO‐Bindungsordnungen und problematische Oxidationsstufenzuordnungen hinweisen 83–85.…”

Section: Non‐innocent Liganden: Nitrosylunclassified

Die Oxidationsstufe, ein Dauerbrenner!

Karen

2015

Angewandte Chemie

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Was ist eine Oxidationsstufe? Die Oxidationsstufe ist durch Algorithmen definiert, ihr fehlt aber eine umfassende Definition. Die Ergebnisse des IUPAC‐Projekts, das versuchen wollte, sich dieser Definition anzunähern, wurden kürzlich in einem technischen Bericht veröffentlicht. Hier wird nun eine Zusammenfassung gegeben, mit Anwendungen an Lewis‐, Bindungsgraph‐ und Summenformeln, zusammen mit neuesten Informationen über schwierige Fälle.

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A distinctly bent metal-nitrosyl bond. The preparation and structure of chlorocarbonylnitrosylbis(triphenylphosphine)iridium tetrafluoroborate, [IrCl(CO)(NO)(P(C6H5)3)2][BF4]

Cited by 65 publications

References 5 publications

Oxidation State, A Long‐Standing Issue!

Oxidation State, A Long‐Standing Issue!

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Die Oxidationsstufe, ein Dauerbrenner!

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