13C and (15)N NMR Mechanistic Study of Cyanide Exchange on Oxotetracyanometalate Complexes of Re(V), Tc(V), W(IV), Mo(IV), and Os(VI).

Abstract

A range of complexes with general formula [MO(X)(CN)(4)](n)()(-) of W(IV), Mo(IV), Re(V), Tc(V), and Os(VI) were prepared and characterized by (13)C, (15)N, (17)O, and (99)Tc NMR, utilizing (13)C- and (15)N-enriched cyano complexes. A correlation between M-O and M-CN bond strength from X-ray crystallographic data and |(1)J((183)W-(13)C)| coupling is reported. The cyanide (HCN/CN(-)) exchange kinetics on the trans-dioxotetracyanometalate complexes and protonated/substituted ([MO(X)(CN)(4)](n)()(-)) forms thereof were studied in aqueous medium. The dioxotetracyano complexes show a trend of reactivity M(IV) > M(V) >M(VI), which is in agreement with the increase in M-L bond strength (L = O(2)(-) or CN(-)) and a dissociative activation for the cyanide and the oxygen exchange in these complexes. Rate constants (X, k(Xc)) in s(-)(1) at 298 K for the [MO(X)(CN)(4)](n)()(-) complexes are as follows for Mo(IV): O(2)(-), >0.4; OH(-), (1.7 +/- 0.1) x 10(-)(2); H(2)O, (1.5 +/- 0.1) x 10(-)(2); CN(-), (9.6 +/- 0.8) x 10(-)(3). For W(IV): O(2)(-), (4.4 +/- 0.4) x 10(-)(3); OH(-), (9.6 +/- 0.9) x 10(-)(5); H(2)O, (1.1 +/- 0.1) x 10(-)(4); CN(-), (1.1 +/- 0.1) x 10(-)(2); N(3)(-), (3.1 +/- 0.2) x 10(-)(4); F(-), (4.8 +/- 0.1) x 10(-)(5). For Tc(V): O(2)(-), (4.8 +/- 0.4) x 10(-)(3); H(2)O, <4 x 10(-)(5); NCS(-), <4 x 10(-)(5). For Re(V): O(2)(-), (3.6 +/- 0.3) x 10(-)(6) and (1.2 +/- 0.1) x 10(-)(4) for CN(-) and HCN, respectively; OH(2), <4 x 10(-)(8). For Os(VI): O(2)(-), <4 x 10(-)(9) and (1.2 +/- 0.1) x 10(-)(4) for CN(-) and HCN, respectively. The cyanide exchange kinetics were correlated with previously determined proton and oxygen exchange, spanning a kinetic domain of more than 12 orders of magnitude for the five metal centers studied.