Single crystal neutron diffraction study of the complex [Ru(H...H) (C{sub 5}Me{sub 5}) (dppm)]BF{sub 4} which contains an elongated dihydrogen ligand
- Brookhaven National Lab., Upton, NY (United States)
- Hong Kong Univ. of Science and Technology (Hong Kong)
- Univ. of Toronto, Ontario (Canada)
- Universita di Milano (Italy)
The H-H distance of the dihydrogen ligand in [Ru(H....H)(C{sub 5}Me{sub 5})(dppm)]BF{sub 4} is 1.08(3) A as determined by neutron diffraction on a crystal of volume 3.2 mm{sup 3} at 15 K: monoclinic, space group P2{sub 1}, a = 10.833(3), b = 15.045(4), c = 10.781(2) A, {beta} = 114.47(2){degree}, V = 1599.3(7) A{sup 3}, and D{sub c} = 1.473 g cm{sup -3} for Z = 2; R(F) = 0.071, R(F{sup 2}) = 0.151, R{sub w}(F{sup 2}) = 0.099 for 4198 reflections. The H-H distance, when corrected for the effects of thermal motion, lengthens slightly from 1.08(3) to 1.10(3) A. The complex contains an elongated dihydrogen ligand which is symmetrically, side-on bonded to the ruthenium as one leg of a three-legged piano stool structure. The H{sub 2} ligand lies parallel to the C{sub 5}Me{sub 5} ligand plane, an orientation where {pi}-overlap with an orbital on the metal is optimum. The T{sub 1} NMR method gives an H H distance of 1.10(1) A for the case of restricted rotation. The present structure provides a model for coordinated H{sub 2} at an intermediate stage of oxidative addition. The {sup 1}J(H, D) coupling in the Ru(H-D) isotopomer increases with decreasing temperature: this is interpreted as a slight shortening of the H-D distance. The structural and {sup 1}H NMR data are compared for dihydrogen complexes which have been studied by single crystal neutron diffraction. 34 refs., 3 figs., 4 tabs.
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- DOE Contract Number:
- AC02-76CH00016
- OSTI ID:
- 102759
- Journal Information:
- Journal of the American Chemical Society, Vol. 116, Issue 17; Other Information: PBD: 24 Aug 1994
- Country of Publication:
- United States
- Language:
- English
Similar Records
Single-crystal X-ray and neutron diffraction studies of an. eta. sup 2 -dihydrogen transition-metal complex: trans-(Fe(. eta. sup 2 -H sub 2 )(H)(PPh sub 2 CH sub 2 CH sub 2 PPh sub 2 ) sub 2 )BPh sub 4
Sterically demanding aryloxides as supporting ligands in organoactinide chemistry. Synthesis, structural characterization, and reactivity of Th(O-2,6-t-Bu{sub 2}C{sub 6}H{sub 3}){sub 2}(CH{sub 2}SiMe{sub 3}){sub 2} and formation of the trimeric thorium hydride Th{sub 3}H{sub 6}(O-2,6-t-Bu{sub 2}C{sub 6}H{sub 3}){sub 6}