Issue 14, 2001
From the journal:

Journal of the Chemical Society, Dalton Transactions

Reactivity of nitrido-carbonyl clusters: synthesis and solid state structure of [Fe5MnN(CO)16]2− and [Fe6N(CO)14NO]2−; oxidation of a cluster-coordinated nitride

Roberto Della Pergola,*a   Luigi Garlaschelli,b   Mario Manassero,*c   Mirella Sansoni,c   Donatella Strumolo,b   Fabrizia Fabrizi de Bianid  and  Piero Zanellod  

* Corresponding authors

a Dipartimento di Scienze dell' Ambiente e del Territorio, Università di Milano Bicocca, piazza della Scienza 1, 20126 Milano, Italy
E-mail: roberto.dellapergola@unimib.it

b Dipartimento di Chimica Inorganica, Metallorganica ed Analitica and centro CSSMTBO del CNR, Università di Milano, via G. Venezian 21, 20133 Milano, Italy

c Dipartimento di Chimica Strutturale e Stereochimica Inorganica, Università di Milano, via G. Venezian 21, 20133 Milano, Italy
E-mail: m.manassero@csmtbo.mi.cnr.it

d Dipartimento di Chimica dell' Università, via A. Moro, 53100 Siena, Italy

Abstract

The cluster [Fe5MnN(CO)16]2− (1) was synthesized from [Fe6N(CO)15]3− and Mn2(CO)10, in refluxing EtCN, or [Fe4N(CO)12]− and [FeMn(CO)9]−. Its solid state structure was determined on the [Me3NCH2Ph]+ salt, and consists of an octahedral metal cage, enclosing a six-coordinated nitrido ligand. The position of the manganese atom in the solid state could be established, despite some crystallographic disorder, by considering the local stereochemistry of the ligands. The cluster [Fe6N(CO)14NO]2− (2) was obtained in moderate yields by the reaction of [Fe4N(CO12]− with Mo(CO)3(EtCN)3. The nitrosyl is formed by oxidation of the starting nitride, and the source of the oxygen is presumably a carbonyl, whose splitting is mediated by the molybdenum complex. This process is the first example of an oxidation of a nitride in a carbonyl cluster. The solid state structure of the iron cluster is also octahedral, and the linear nitrosyl ligand was unambiguously located from the short Fe–N bond distance, and from dishomogeneous distribution of ligands. Cyclic voltammetric studies have shown that electron transfer processes are followed by chemical reactions thus testifying that no stable redox congeners exist for these two nitride clusters.

Graphical abstract: Reactivity of nitrido-carbonyl clusters: synthesis and solid state structure of [Fe5MnN(CO)16]2− and [Fe6N(CO)14NO]2−; oxidation of a cluster-coordinated nitride

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Article information

DOI
https://doi.org/10.1039/B100148P
Article type
Paper
Submitted
02 Jan 2001
Accepted
21 May 2001
First published
19 Jun 2001

J. Chem. Soc., Dalton Trans., 2001, 2179-2183

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Reactivity of nitrido-carbonyl clusters: synthesis and solid state structure of [Fe5MnN(CO)16]2− and [Fe6N(CO)14NO]2−; oxidation of a cluster-coordinated nitride

R. D. Pergola, L. Garlaschelli, M. Manassero, M. Sansoni, D. Strumolo, F. F. de Biani and P. Zanello, J. Chem. Soc., Dalton Trans., 2001, 2179 DOI: 10.1039/B100148P

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