Structural analysis of the coordination of dinitrogen to transition metal complexes

Author(s):  
Benjamin Peigné ◽  
Gabriel Aullón

Transition-metal complexes show a wide variety of coordination modes for the nitrogen molecule. A structural database study has been undertaken for dinitrogen complexes, and geometrical parameters around theLnM—N2unit are retrieved from the Cambridge Structural Database. These data were classified in families of compounds, according to metal properties, to determine the degree of lengthening for the dinitrogen bonding. The importance of the nature of the metal center, such as coordination number and electronic configuration, is reported. Our study reveals poor activation by coordination of dinitrogen in mononuclear complexes, always havingend-oncoordination. However, partial weakening of nitrogen–nitrogen bonding is found forend-onbinuclear complexes, whereasside-oncomplexes can be completely activated.

2015 ◽  
Vol 26 (5-6) ◽  
pp. 1715-1723 ◽  
Author(s):  
Javier Fernández-Valparís ◽  
Santiago Alvarez

Author(s):  
Dušan P. Malenov ◽  
Jelena P. Blagojević Filipović ◽  
Snežana D. Zarić

In the crystal structures of methylated cyclopentadienyl (Cp) complexes (MeCp, Me4Cp and Me5Cp) deposited in the Cambridge Structural Database, certain orientation types of stacked contacts can be noted as the most frequent. These orientation preferences can be well explained by the matching of oppositely charged regions of electrostatic potential. Parallel displaced stacking, large offset stacking and C—H...π interactions are the dominant interaction types that are responsible for the arrangement in the crystal structures of stacked methylated Cp complexes.


2021 ◽  
Author(s):  
Yuya Ashida ◽  
Yoshiaki Nishibayashi

Nitrogen fixation using homogeneous transition metal complexes under mild reaction conditions is a challenging topic in the field of chemistry. Several successful examples of the catalytic conversion of nitrogen molecule...


1984 ◽  
Vol 39 (9) ◽  
pp. 1268-1275 ◽  
Author(s):  
Dieter Sellmann ◽  
Wolfgang Reißer

Alkylation of [Fe(CO)2(S2C6H4)2]2- by Br(CH2)nBr (n = 1,3-6) or CICH2COCH2Cl yields [Fe(CO)2(C6H4S2-(CH2)n-S2C6H4)] and [Fe(CO)2(C6H4S2-CH2COCH2-S2C6H4)]. respectively. With long-chain dibromoalkanes (n = 7,8,12) the oligonuclear complexes [Fe(CO)2(C6H4S2 - (CH2)n - S2C6H4)]x also form; in these cases the mononuclear complexes can be obtained by dilution methods. Growing length of the bridge between the thioether donor atoms favours the loss of CO and formation of [Fe(CO)(C6H4S2-(CH2)3-S2C6Η4)]2 and [Fe(C6H4S2 - (CH2)n-S2C6H4)]x (n = 1,4-8,12). respectively; substitution rate of CO by PMe3 is increased as well. Hydrolysis of the Fe(CO)2 complexes by HCl gives the free tetradentate thioetherthiol ligands HSC6H4S - (CH2)n - S2C6H4SH.


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