In:
Zeitschrift für anorganische und allgemeine Chemie, Wiley, Vol. 646, No. 22 ( 2020-11-30), p. 1820-1833
Abstract:
The synthesis of [Ti 6 O 4 (O i Pr) 8 (O 2 CPh) 8 ] ( 3 ) and [RuCl(N≡CR) 5 ][RuCl 4 (N≡CR) 2 ] ( 4a , R = Me; 4b , R = Ph), [Ru(N≡CPh) 6 ][RuCl 4 (N≡CPh) 2 ] ( 5 ) and [H 3 O][RuCl 4 (N≡CMe) 2 ] ( 7a ) is discussed. Crystallization of 5 from CH 2 Cl 2 gave trans ‐[RuCl 2 (N≡CPh) 4 ] ( 6 ). The solid‐state structures of 3 , 4a , b , 5 , 6 and 7a are reported. Complex 4b forms a 3D network, while 6 displays a 2D structure, due to π‐interactions between the benzonitrile ligands. The (spectro)electrochemical behavior of 4a , b and 6 was studied at 25 and –72 °C and the results thereof are compared with [NEt 4 ][RuCl 4 (N≡CMe) 2 ] ( 7b ) and [RuCl(N≡CPh) 5 ][PF 6 ] ( 8 ). The electrochemical response of the cation and the anion in 4a , b are independent from each other. [RuCl(N≡CR) 5 ] + possesses one reversible Ru II /Ru III process. However, [RuCl 4 (N≡CMe) 2 ] – was shown to be prone to ligand exchange and disproportionation upon formation of either a Ru IV and Ru II species at 25 °C, while at –72 °C the rapid conversion of the electrochemically formed species is hindered. In situ IR and UV/Vis/NIR studies confirmed the respective disproportionation reaction products of the aforementioned oxidation and reduction, respectively.
Type of Medium:
Online Resource
ISSN:
0044-2313
,
1521-3749
DOI:
10.1002/zaac.v646.22
DOI:
10.1002/zaac.202000304
Language:
English
Publisher:
Wiley
Publication Date:
2020
detail.hit.zdb_id:
201094-X
detail.hit.zdb_id:
1481139-X
Bookmarklink