“Guilty” Verdict—Evidence for the Noninnocence of Cyanide

Kaim, Wolfgang

doi:10.1002/anie.201105767

Cited by 24 publications

(22 citation statements)

References 55 publications

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“…[{L n M}{-(CC) n }ML n ] n+ have been reviewed on several previous occasions[187,[210][211][212][213] so only a brief summary is presented here. The C 2 moiety represents the most elementary carbon-based bridging ligand beyond carbide complexes[214,215], and has a close structural and electronic relationship with the ubiquitous, but still fascinating, conjugated bridging ligand, cyanide[216,217]. Despite the large number of complexes with -CN ligands and the substantial number of studies of the redox chemistry and CN mediated charge transfer processes within these systems, it is only relatively recently that the redox chemistry, electronic structure and intramolecular charge transfer properties of -C 2 complexes have been explored[218].…”

mentioning

confidence: 99%

Twists and turns: Studies of the complexes and properties of bimetallic complexes featuring phenylene ethynylene and related bridging ligands

Low

2013

Coordination Chemistry Reviews

159

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The concept of a molecular-based electronic technology has been evolving for over 50 years, and the development of molecular designs for such components over this period has drawn heavily on studies of intramolecular charge transfer in mixed-valence complexes and related systems. Recent advances in methods for the assembly and measurement of device characteristics of metal|molecule|metal junctions have brought the realisation of the considerable promise of the area within a tantalisingly close reach. This review presents a selective review of the chemistry, spectroscopic properties and electronic structures of bimetallic complexes [{LxM}(μ-bridge){MLx}]n+ based primarily, but not exclusively, on the Ru(PP)Cp' and Mo(dppe)(η-C7H7) fragments and alkynyl based bridging ligands. The molecular design strategies that lead to a wide spectrum of electronic characteristics in these systems are described. Examples range from weakly coupled mixed-valance complexes through more strongly coupled systems in which the electronic states of the bridging ligand are intimately involved in electron transfer processes to complexes. An argument is made that the latter are better described in terms of redox non-innocent bridging ligands supported by metal-based donor substituents rather than strongly coupled mixed valence complexes. The significance of these results on the further development of metal complexes for use as components within a hybrid molecular electronics technology are discussed.

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mentioning

confidence: 99%

Twists and turns: Studies of the complexes and properties of bimetallic complexes featuring phenylene ethynylene and related bridging ligands

Low

2013

Coordination Chemistry Reviews

159

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“…In this regard, Kaim pointed out the non‐innocent nature of CN − . [5] Comparable rhodates and iridates reported later displayed similar features. [6] This bonding scheme is well‐known in carbonyl chemistry containing carbon monoxide isoelectronic to CN − : [7] Non‐innocent CO ligands are able to stabilize transition metal oxidation states as low as −IV, for example, in [Cr(CO) 4 ] 4− , which is the lowest transition metal oxidation state known so far.…”

Section: Introductionmentioning

confidence: 68%

“…The complex is therefore better described as [Co − (CN 1.67− ) 3 ], instead of the purely formal notation [Co −III (CN − ) 3 ] 6− . In this regard, Kaim pointed out the non‐innocent nature of CN − [5] . Comparable rhodates and iridates reported later displayed similar features [6] .…”

Section: Introductionmentioning

confidence: 88%

Tricyanidoferrates(−IV) and Ruthenates(−IV) with Non‐Innocent Cyanido Ligands

et al. 2021

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Exceptionally electron‐rich, nearly trigonal‐planar tricyanidometalate anions [Fe(CN)3]7− and [Ru(CN)3]7− were stabilized in LiSr3[Fe(CN)3] and AE3.5[M(CN)3] (AE=Sr, Ba; M=Fe, Ru). They are the first examples of group 8 elements with the oxidation state of −IV. Microcrystalline powders were obtained by a solid‐state route, single crystals from alkali metal flux. While LiSr3[Fe(CN)3] crystallizes in P63/m, the polar space group P63 with three‐fold cell volume for AE3.5[M(CN)3] is confirmed by second harmonic generation. X‐ray diffraction, IR and Raman spectroscopy reveal longer C−N distances (124–128 pm) and much lower stretching frequencies (1484–1634 cm−1) than in classical cyanidometalates. Weak C−N bonds in combination with strong M−C π‐bonding is a scheme also known for carbonylmetalates. Instead of the formal notation [Fe−IV(CN−)3]7−, quantum chemical calculations reveal non‐innocent intermediate‐valent CN1.67− ligands and a closed‐shell d10 configuration for Fe, that is, Fe2−.

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“…Although not strictly an organometallic ligand, cyanide is often discussed in analogy to isoelectronic CO . However, the sometimes invoked π acceptor character of cyanide is little pronounced, as evident from the rarity of reduced cyanide in metal complexes; one first such recent example is M 3 [Co(CN) 3 ], M = Sr or Ba, with an experimentally and theoretically evidenced 18 VE and d 10 configuration of cobalt(–I) and three CN –1.67 ligands , …”

Section: Organoligand‐based Electron Transfermentioning

confidence: 99%

Sites of Electron Transfer Reactivity in Organometallic Compounds

Kaim

2020

Eur J Inorg Chem

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Three essentially different sites are identified for redox activity in organometallic compounds: The metal, the organometallic (C‐bonded) ligand(s), and potentially noninnocent co‐ligands. Typical reactivity patterns resulting from either of these alternatives will be pointed out by means of representative examples, possibly involving unusual metal oxidation states, carbon‐centered radicals, or ligand redox systems.

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“Guilty” Verdict—Evidence for the Noninnocence of Cyanide

Cited by 24 publications

References 55 publications

Twists and turns: Studies of the complexes and properties of bimetallic complexes featuring phenylene ethynylene and related bridging ligands

Twists and turns: Studies of the complexes and properties of bimetallic complexes featuring phenylene ethynylene and related bridging ligands

Tricyanidoferrates(−IV) and Ruthenates(−IV) with Non‐Innocent Cyanido Ligands

Sites of Electron Transfer Reactivity in Organometallic Compounds

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