Neutral Carbonyl Complexes Research Articles

Desymmetrization of an Octahedral Coordination Complex Inside a Self-Assembled Exoskeleton.

The synthesis of a centrally functionalized, ribbon-shaped [6]polynorbornane ligand L that self-assembles with Pd(II) cations into a {Pd2 L4 } coordination cage is reported. The shape-persistent {Pd2 L4 } cage contains two axial cationic centers and an array of four equatorial H-bond donors pointing directly towards the center of the cavity. This precisely defined supramolecular environment is complementary to the geometry of classic octahedral complexes [M(XY)6 ] with six diatomic ligands. Very strong binding of [Pt(CN)6 ](2-) to the cage was observed, with the structure of the host-guest complex {[Pt(CN)6 ]@Pd2 L4 } supported by NMR spectroscopy, MS, and X-ray data. The self-assembled shell imprints its geometry on the encapsulated guest, and desymmetrization of the octahedral platinum species by the influence of the D4h -symmetric second coordination sphere was evidenced by IR spectroscopy. [Fe(CN)6 ](3-) and square-planar [Pt(CN)4 ](2-) were strongly bound. Smaller octahedral anions such as [SiF6 ](2-) , neutral carbonyl complexes ([M(CO)6 ]; M=Cr, Mo, W) and the linear [Ag(CN)2 ](-) anion were only weakly bound, showing that both size and charge match are key factors for high-affinity binding.

Mutual Catalysis of Neutral and Anionic Cobalt Carbonyls in Their CO Scrambling Reactions

Redox‐condensation equilibria, probably with the participation of [Co3(CO)10]− as intermediate, and not ion pairing as previously postulated, explain the acceleration of the CO scrambling in [Co(CO)4]− by alkali metal counterions. The studies described here show that neutral carbonyl complexes catalyze the CO scrambling for anionic metal carbonyls and vice versa, and that the catalysis is less effective in the presence of free CO. The latter is in agreement with [Co3(CO)10]− as the intermediate. These results are important mainly because neutral and anionic metal carbonyls frequently exist together as a result of side reactions.

ChemInform Abstract: IRON‐CONTAINING METALLOPHOSPHAZENES AND THEIR CLUSTERS DERIVED FROM CHLOROPHOSPHAZENES AND ORGANOMETALLIC DIANIONS

AbstractDie Perchlorocyclophosphazene (I) und (IV) reagieren mit Dinatriumoctacarbonyldiferrat zu den Dieisen‐ und Trieisencyclophosphazen‐Komplexen (II) oder (V) bzw. (III) oder (VI).

Iron-containing metallophosphazenes and their clusters derived from chlorophosphazenes and organometallic dianions

Abstract : Hexachlorocyclotriphosphazene, (NPCi2)3, reacts with disodium octacarbonyldikferrate, Na2Fe2(CO)8, to yield the diiron and triiron cyclotriphosphazene complexes. The analogous cyclic tetramer (NPCl2)4 reacts similarly to yield the diiron and triiron analogues 5 and 6, respectively. Compounds 2 and 5 are the first chlorophosphazenes that contain two metal-phosphorus covalent bonds and a three-membered spirocyclic ring at phosphorus. Compound 3 can also be obtained by the thermal reaction of 2 with the neutral carbonyl complexes Fe(CO)5 and Fe2(CO)9. In addition, the thermal reaction of 2 with Ru3(CO)12 yields the mixed-metal cluster 7, similar in structure to 3, but with a Ru(CO)3 unit in place of the nitrogen-bound Fe(CO)3. The trimetallic clusters 3, 6, and 7 are the first phosphazene compounds in which a portion of the phosphazene ring has been incorporated into a metallic cluster unit. Compounds 3, 6, and 7 contain both phosphorus-metal and nitrogen-metal bonds, demonstrating both the covalent and coordinative capacities of phosphazene rings. The new metallophosphazenes were characterized by 31P NMR, Mossbauer, infrared, and mass spectral techniques by X-ray crystal structure analyses. Originator supplied keywords include: Cyclophosphazenes, Metallic clusters, Metallophosphazenes, and Mossbauer spectroscopy.

Organometallic nitrosyl chemistry. 4. Additional reactions of nitrosyl chloride with neutral carbonyl complexes

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTOrganometallic nitrosyl chemistry. 4. Additional reactions of nitrosyl chloride with neutral carbonyl complexesBrian W. S. Kolthammer, Peter. Legzdins, and John T. MalitoCite this: Inorg. Chem. 1977, 16, 12, 3173–3178Publication Date (Print):December 1, 1977Publication History Published online1 May 2002Published inissue 1 December 1977https://doi.org/10.1021/ic50178a038RIGHTS & PERMISSIONSArticle Views112Altmetric-Citations20LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (901 KB) Get e-Alerts Get e-Alerts

The electronic structure of transition metal carbonyl complexes

Discrete variational X α calculations are reported on the neutral carbonyl complexes Ni(CO)4, Fe(CO)5 and Cr(CO)6, as well as on the ions Co(CO)4 -, Fe(CO)4 -, Mn(CO)5 -, Mn(CO)6 + and V(CO)6 -. Valence electron ionization potentials are predicted very well by transition-state calculations. The description of complex binding in Ni(CO)4 according to these calculations differs markedly from the one obtained in MSXα and Hartree-Fock calculations, which contradicted each other. The relative magnitude of σ-donation and π-back-donation is found to be roughly equal in the three neutral complexes (0·2–0·3 and 0·5 e respectively). Large changes occur in the ionic complexes, notably in the π-back-donation. These changes are correlated with the observed shifts in C-O stretching frequencies and force constants.

Organometallic nitrosyl chemistry. I. Reactions of nitrosyl chloride with some anionic and neutral carbonyl complexes

Organometallic nitrosyl chemistry. I. Reactions of nitrosyl chloride with some anionic and neutral carbonyl complexes