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Carbonyl‐Nitrido Mixed‐Metal Clusters: Synthesis, Reactivity, Electrochemical Behavior and Solid‐State Structure of [Co 5 MoN(CO) 14 ] 2− and [Co 5 MoN(CO) 14 AuPPh 3 ] −
Author(s) -
Della Pergola Roberto,
Fumagalli Alessandro,
Fabrizi de Biani Fabrizia,
Garlaschelli Luigi,
Laschi Franco,
Malatesta Maria Carlotta,
Manassero Mario,
Roda Elena,
Sansoni Mirella,
Zanello Piero
Publication year - 2004
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200400104
Subject(s) - chemistry , reactivity (psychology) , crystallography , octahedron , acetonitrile , molybdenum , electrochemistry , cluster (spacecraft) , cobalt , metal , ligand (biochemistry) , oxidation state , electron paramagnetic resonance , redox , inorganic chemistry , crystal structure , organic chemistry , medicine , biochemistry , physics , alternative medicine , receptor , electrode , pathology , nuclear magnetic resonance , computer science , programming language
The dianionic cluster [Co 5 MoN(CO) 14 ] 2− ( 1 ) was synthesized from [Co 6 N(CO) 15 ] − and [Mo 2 (CO) 10 ] 2− in refluxing acetonitrile. The solid‐state structure of the [Ph 4 P] + salt was determined. It consists of an octahedral metal cage, enclosing a six‐coordinate nitrido ligand. Typical bond lengths are: Co−N 1.88 Å, Mo−N 2.03 Å, Co−Co 2.61 Å and Co−Mo 2.84 Å, showing that there is very little, if any, preferential interaction of the interstitial atom with that of molybdenum. The cluster reacts with Au(PPh 3 )Cl in THF at room temperature forming the derivative [Co 5 MoN(CO) 14 {AuPPh 3 }] − ( 2 ). The gold atom caps an MoCo 2 face of the octahedron, with short Au−Co (2.68 Å) and long Au−Mo (3.16 Å) bonds, showing that both metal atoms are necessary for coordination, but Au I binds better with the cobalt atoms. Electrochemical studies have pointed out that cluster 1 has good redox capabilities in that it is able to support reversibly the progressive addition of three electrons. EPR measurements on the corresponding trianion confirm the lack of preferential interaction between the Mo site and the interstitial nitride atom. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)