Coordination compounds of the same composition but differing connectivity to ligands
In chemistry, linkage isomerism or ambidentate isomerism is a form of isomerism in which certain coordination compounds have the same composition but differ in their metal atom's connectivity to a ligand.
Typical ligands that give rise to linkage isomers are:
cyanide, CN− – isocyanide, NC−
cyanate, OCN− – isocyanate, NCO−
thiocyanate, SCN− – isothiocyanate, NCS−
selenocyanate, SeCN− – isoselenocyanate, NCSe−
nitrite, NO−2
sulfite, SO2−3
Examples of linkage isomers are violet-colored [(NH3)5Co-SCN]2+ and orange-colored [(NH3)5Co-NCS]2+. The isomerization of the S-bonded isomer to the N-bonded isomer occurs intramolecularly.[1]
The complex cis-dichlorotetrakis(dimethylsulfoxide)ruthenium(II) (RuCl2(dmso)4) exhibits linkage isomerism of dimethyl sulfoxide ligands due to S- vs. O-bonding. Trans-dichlorotetrakis(dimethylsulfoxide)ruthenium(II) does not exhibit linkage isomers.
^Buckingham, D. A.; Creaser, I. I.; Sargeson, A. M. (1970). "Mechanism of Base Hydrolysis for CoIII(NH3)5X2+ Ions. Hydrolysis and Rearrangement for the Sulfur-Bonded Co(NH3)5SCN2+ Ion". Inorg. Chem.9 (3): 655–661. doi:10.1021/ic50085a044.
In chemistry, linkageisomerism or ambidentate isomerism is a form of isomerism in which certain coordination compounds have the same composition but...
yellow = S. Structure of Pd(Me2N(CH2)3PPh2)(SCN)(NCS) illustrating linkageisomerism of the SCN- ligand.. Crystal structure of [ReIV(NCS)5(SCN)]2-. Color...
forms of isomerism are structural (or constitutional) isomerism, in which bonds between the atoms differ; and stereoisomerism or (spatial isomerism), in which...
isomerism, solvate or hydrate isomerism, linkageisomerism and coordination isomerism. Ionisation isomerism – the isomers give different ions in solution...
ISBN 3-527-30673-0. Angus, Patricia M.; Jackson, W. Gregory (1994). "LinkageIsomerism in Cobalt(III) Pentaammine Complexes of 2-Pyridone". Inorganic Chemistry...
factors, e.g. kinetics and solubility, are sometimes involved, and linkageisomerism can occur, for example [Co(NH3)5(NCS)]Cl2 and [Co(NH3)5(SCN)]Cl2....
the sulfur atom or the nitrogen atom. Such compounds give rise to linkageisomerism. Polydentate and ambidentate are therefore two different types of...
amino acid sequencing in the Edman degradation. Isothiocyanate and its linkageisomer thiocyanate are ligands in coordination chemistry. Thiocyanate is a...
Materials Manifested in Molecular Complexes: Observation of Cyanide LinkageIsomerism and Spin-Crossover Behavior in Pentanuclear Cyanide Clusters". J....
nitrogen cycle. Three linkageisomers are common for nitrite ligands, O-bonded, N-bonded, and bidentate O,O-bonded. The former two isomers have been characterized...
yellow complex Rh(PPh3)3(NCO) and orange complex Rh(PPh3)3(OCN) are linkageisomers and show differences in their infrared spectra which can be used for...
metals by the oxygen atom or by sulfur. This dichotomy is called linkageisomerism. O-bonded sulfoxide ligands are far more common, especially for 1st...
second linkageisomers is also known. In the second isomer one of the acetylacetonate ligands is bonded to Ir through carbon. The O6-bonded isomer has been...
Todorova, Teodora; Delley, Bernard (2009). "Photogeneration of Nitrosyl LinkageIsomers in Octahedrally Coordinated Platinum Complexes in the Red Spectral...
anions and their interactions in nitropentaamminecobalt(III) toward linkageisomerism-induced photochemical motion". International Journal of Quantum Chemistry...
Schaniel, Dominik (2019). "Room‐Temperature Photogeneration of Nitrosyl LinkageIsomers in Ruthenium Nitrosyl Complexes" (PDF). Chemistry – A European Journal...
=0^{\circ }} for the cis isomer (synperiplanar conformation), and ω = 180 ∘ {\displaystyle \omega =180^{\circ }} for the trans isomer (antiperiplanar conformation)...
interactions at low temperatures. Ir(acac)3 and Rh(acac)3 are known. A second linkageisomer of the iridium complex is known, trans-Ir(acac)2(CH(COMe)2)(H2O). This...
been characterized. These complexes exist in either the N or the O linkageisomers. It can be assumed that such monodentate complexes exist transiently...
nitrogen atoms with molecular formula C2H3N3. Triazoles exhibit substantial isomerism, depending on the positioning of the nitrogen atoms within the ring. Many...
molecules). For example, the aldohexose glucose may form a hemiacetal linkage between the aldehyde group on carbon 1 and the hydroxyl on carbon 4, yielding...
derivative of norbornene. Nadic anhydride exhibits endo-exo isomerism. In the exo isomer, the acid anhydride group points in the same direction towards...
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