Iminic N-bound iminophosphorano versus nitrilic n-bound iminophosphorano Os(IV) complexes: a new double derivatization of the nitrido ligand.
The reactions between trans-[Os(IV)(tpy)(Cl)(2)(NCN)] (1) and PPh(3) and between trans-[Os(IV)(tpy)(Cl)(2)(NPPh(3))](+) (2) and CN(-) provide new examples of double derivatization of the nitrido ligand in an Os(VI)-nitrido complex (Os(VI)N). The nitrilic N-bound product from the first reaction, trans-[Os(II)(tpy)(Cl)(2)(NCNPPh(3))] (3), is the coordination isomer of the first iminic N-bound product from the second reaction, trans-[Os(II)(tpy)(Cl)(2)(N(CN)(PPh(3)))] (4). In CH(3)CN at 45 degrees C, 4 undergoes isomerrization to 3 followed by solvolysis and release of (N-cyano)iminophosphorane, NCNPPh(3). These reactions demonstrate new double derivatization reactions of the nitrido ligand in Os(VI)N with its implied synthetic utility.
Huynh
My Hang V
MH
Dynamic Experimentation Division, DX-2: Materials Dynamics Group, Los Alamos National Laboratory, New Mexico 87545, USA. huynh@lanl.gov
Meyer
Thomas J
TJ
Jameson
Donald L
DL