Electronic structure and bonding in manganese pentacarbonyl halides and hydride

Influence parameters. A quantitative characteristics of the capacity of ligands to exert mutual influence

Infrared intesities of the carbonyl stretching modes in bipyramidal cobalt and iron tetracarbonyl compounds

19 – Bonding of Unsaturated Organic Molecules to Transition Metals

ClMn(CO)4P(C6H5)3 kristallisiert triklin mit zwei Molekulen in der Elementarzelle. Das Manganatom hat oktaedrische Koordination. Das Molekul besitzt die schon aus seinem IR-Spektrum abgeleitete cis-Anordnung der Liganden. Die Abstande MnCl (2.36 A) und MnP (2.40 A) entsprechen recht genau den geschatzten Einfachbindungslangen. Demnach tritt keine relevante MnP-Ruckbindung auf, und der π-Bindungsanteil ist hier auf die beiden dem Chlor und Phosphor gegenuberliegenden sehr kurzen (1.75 A) MnC-Bindungen lokalisiert. Dagegen verteilt sich bei den beiden anderen, zueinander trans-standigen CO-Gruppen die Ruckbindung auf beide Mn–C-Bindungen (durchschnittlich 1.84 A), die dadurch um 0.09 A langer werden.



The trans-Effect in Octahedral Complexes: Crystal Structure of ClMn(CO)4P(C6H5)3



ClMn(CO)4P(C6H5)3 crystallizes in the triclinic system with two molecules in the unit cell. The coordination of the manganese atom is octahedral. The cis arrangement of ligands already deduced from the i. r. spectrum of the molecule is confirmed. The distances MnCl (2.36 A) and MnP (2.40 A) correspond closely to the estimated single bond lengths. Therefore no relevant MnP back donation occurs, and the π-bonding component is localized in the two very short (1.75 A) MnC bonds lying opposite to the chlorine and phosphorus atoms. On the other hand the two other CO groups, which are trans to each other, share the back donation, so that these two MnC bonds (average 1.84 A) become 0.09 A longer.

Electronic structure and bonding in manganese pentacarbonyl halides and hydride

Citations

Influence parameters. A quantitative characteristics of the capacity of ligands to exert mutual influence

Infrared intesities of the carbonyl stretching modes in bipyramidal cobalt and iron tetracarbonyl compounds

19 – Bonding of Unsaturated Organic Molecules to Transition Metals

Zum trans-Effekt an oktaedrischen Komplexen: Die Kristallstruktur von ClMn(CO)4P(C6H5)3

Molecular orbital theory of transition metal complexes

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