
TY  - JOUR
A1  - Alcock, NW 
A1  - Creaser, II 
A1  - Curtis, NJ 
A1  - Roecker, L 
A1  - Sargeson, AM 
A1  - Willis, AC 
T1  - Intramolecular Hydrolysis of Coordinated Acetonitrile in a Binuclear Complex of Cobalt(III): X-Ray Crystallographic Analysis of Salts of [(tren)Co(&#956;-NH<sub>2</sub>,&#956;-L)Co(tren)]<sup>4+</sup>(L=OH, CH<sub>3</sub>C(O)NH)
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1990
VL  - 43
IS  - 4
SP  - 643
EP  - 654
KW  - 
UR  - https://doi.org/10.1071/CH9900643 
N2  - A synthesis of [( tren )Co(&#956;-NH2,&#956;-OH)Co( tren )]4+(3)( tren = tris (2- aminoethyl )amine) is reported along with a series of derivatives: [( tren ) XCo (&#956;-NH2) CoX ( tren )]n+, where X = CF3SO3- (n = 3)(4), X = CH3CN (n = 5)(5), and [( tren )Co(&#956;-NH2,&#956;-CH3C(O)NH)Co( tren )]4+ (6). The substitution of (4) by CH3CN to yield (5) was studied in CH3CN at 20&#176;C, k = 9.0&#215;10-3 s-1, and the intramolecular hydrolysis of (5) to yield the bridging acetamide complex (6) was studied at various acid concentrations. The X-ray crystal structures were determined for (3b) (exafluorophosphate, dihydrate) and (6b) (dithionate, tetrahydrate ). Both crystals are monoclinic, respectively P21/n with a 11.082(2), b 10.402(2), c 15.611(2)&#506;, &#946; 99.13(2)&#176;, Z 2, and C2/c with a 14.328(2), b 14.046(1), c 16.497(2)&#506;, &#946; 101.90(1)&#176;, Z 4. For the salt of (3), 2389 data with 1 &#8805; 2&#963;(I) were refined to R 0.070 ( Rw 0.066), and, for the salt of (6), 3087 data with I &#8805; 3&#963;(I) were refined to R 0.041 ( Rw 0.056). Both ions lie on pseudo-symmetric sites involving disorder of the bridging ligands . The structures establish the binding mode of the acetamido ion and the orientation of the tren groups in the isolated complexes. 
ER  -

