ISSN:
0044-2313
Keywords:
Linkage isomers
;
Pentachloromonothiocyanato(N)-rhenate(IV)
;
Pentachloromonothiocyanato(S)-rhenate(IV)
;
Crystal Structure
;
Normal Coordinate Analysis
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Preparation, Crystal Structure, and Normal Coordinate Analysis of Linkage Isomeric Pentachlororhodanorhenates(IV)By treatment of [ReCl5I]2- with (SCN)2 in dichloromethane the linkage isomers [ReCl5(NCS)]2- and [ReCl5(SCN)]2- are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on single crystals of (n-Bu4N)2[ReCl5(NCS)] (monoclinic, space group P21/n, a = 10.728(5), b = 11.572(5), c = 35.414(5), β = 91.896(5)°, Z = 4) and (n-Bu4N)2[ReCl5(SCN)] (monoclinic, space group P 21/c, a = 15.447(5), b = 31.140(5), c = 19.459(5), β = 109.660(5)°, Z = 8) reveals that the thiocyanate group is bonded with the Re-N-C angle of 170.6° or Re-S-C angles of 104.4° and 106.3°. The IR and Raman spectra of both linkage isomers are assigned by normal coordinate analysis using the molecular parameters of the X-ray determination. The valence force constants are fd(ReN) = 1.72 and fd(ReS) = 1.30 mdyn/Å.
Notes:
Bei der Umsetzung von [ReCl5I]2- mit (SCN)2 in Dichlormethan entstehen die Bindungsisomeren [ReCl5(NCS)]2- und [ReCl5(SCN)]2-, die durch Ionenaustauschchromatographie an Diethylaminoethyl-Cellulose getrennt werden. Die Röntgenstrukturanalyse an Einkristallen von (n-Bu4N)2[ReCl5(NCS)] (monoklin, Raumgruppe P21/n, a = 10,728(5), b= 11,572(5), c = 35,414(5), β = 91,896(5)°, Z = 4) und (n-Bu4N)2[ReCl5(SCN)] (monoklin, Raumgruppe P21/c, a = 15,447(5), b = 31,140(5), c = 19,459(5), β = 109,660(5)°, Z = 8) zeigt, daß die Thiocyanatgruppe unter dem Re—N—C-Winkel von 170,6° bzw. den Re—S—C-Winkeln von 104,4° und 106,3° gebunden ist. Unter Verwendung der röntgenographisch ermittelten Molekülparameter lassen sich die IR- und Raman-Spektren der beiden Bindungsisomeren mit Hilfe einer Normalkoordinatenanalyse zuordnen. Die Valenzkraftkonstanten betragen fd(ReN) = 1,72, und fd(ReS) = l,30 mdyn/Å.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19976230130
