Molecular nitrogen as a ligand. The crystal structure of nitrogenpentaammineruthenium(II) dichloride and related salts

Abstract

The X-ray crystal structure analysis of the chloride of nitrogenpentammineruthenium(II) has been carried out with diffractometer data. The salt crystallizes in the cubic system, a= 10.141/~, space group Fm3m, F432 or F-g3m; these are indistinguishable because all non-hydrogen atoms are in special positions. The structure is disordered, the nitrogen molecule randomly occupying one of the six octahedral positions around the ruthenium ion. Within the limits of accuracy imposed by the disorder, the Ru-N-N moiety is linear. An investigation has been made of the isomorphous bromide (a= 10.41/~), iodide (a= 10.94/~), tetrafluoroborate (a= 11.166 A) and hexafluorophosphate (a= 11-79 A,).

Photogeneration of metastable side-on N2 linkage isomers in [Ru(NH3)5N2]Cl2, [Ru(NH3)5N2]Br2 and [Os(NH3)5N2]Cl2

“…Fig.6shows the calculated structures of the ground state and metastable side-on configuration for the [Os(NH 3 ) 5 N 2 ] 2+ ion. The structures calculated by DFT agree well with the known groundstate crystal structures of RuCl, RuBr and OsCl,33,34 as illustrated by the bond lengths listed in Table3. Structural data of the metastable state are available for [Os(NH 3 ) 5 N 2 ][PF 6 ] 2 ,10 where a lengthening of the Os-N(N 2 ) bond by 0.263(17) A ˚was observed.…”

Benzonitrile and acetonitrile complexes of ruthenium ammines

“…Despite the abnormal negative +CN), we believe that the Ru(II) species reported in this article are of the more typical linear structure D as is the N2 complex [Ru(NH3)6N2]Cl2. 26 The reasoning is based upon several considerations. First, the magnitudes of the y(CN) negative shifts are markedly smaller than in the previous examples of x coordination.…”

Recent advances in the chemistry of nitrogen fixation

“…It shows no particularly unusual features; the N-N distance is 1.12 and the Os-N-N angle Is 178.3°, and, unlike its ruthenium analogue, there are no disorder problems 121. The green dinitrogen-bridged complex[¡OsCI(NH3)4]2(N2)]2+ [y(N2) 1999 cm-1 in its Raman spectrum] has been prepared by the elution, in 3 M HCI solution from an ion-exchange column,122 of the product of heating [Os(NH3)4(N2)2]CI2123 to 70 °C in water.…”