Übergangsmetallkomplexe mit Schwefelliganden, IX. Templat-Synthese und Reaktionen der Eisen(II)-Komplexe [Fe(CO)2(C6H4S2–X–S2C6H4)] mit kurz- und langkettig verbrückten o-Benzoldithiolat-Liganden, X = (CH2)n, n = 1,3–8,12; X = CH2COCH2; Synthese der freien Liganden / Transition Metal Complexes with Sulfur Ligands, IX* Template Synthesis and Reactions of the Iron(II) Complexes [Fe(CO)2(C6H4S2–X–S2C6H4)] with o-Benzenedithiolate Ligands. Bridged by Short as well as Long Chains (X = (CH2)n, n = 1,3–8,12; X = CH2COCH2); Synthesis of the Free Ligands

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.

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.


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