Molecular Dinitrogen Complexes of Ruthenium(II) Porphyrins
Camenzind, M.J., James, B.R., David Dolphin, Sparapany, J.W., and Ibers, J.A.
Photolysis of Ru(TMP)(CO) (TMPH2 = 5,10,15,20-tetramesitylporphyrin) in THF affords Ru(TMP)(THF)2. Exposure of Ru(TMP)(THF)2 in C6H6 to N2 gave Ru(TMP)(THF)(N2). Ru(TMP)L(N2) (L = Et2O, DMF, Et3N) were prepared either by exposure of Ru(TMP)(N2)2 to L or by treatment of Ru(TMP) with L to afford Ru(TMP)L2 and subsequent exposure to N2. Ru(TMP)(THF)(N2) is monoclinic, Z = 4, a 13.617(6), b 17.021(10), c 26.194(10) Å β 94.15o, space group P21/c. In this structure the Ru center is octahedrally coordinated, with the Ru-N-N moiety being trans to the Ru-THF group. The Ru-N2 linkage is linear, with a Ru-N distance of 1.822(13) Å, compared with a Ru-N(porphyrin) average distance of 2.052(10) Å.