TY - JOUR
T1 - Chains of Centered Metal Clusters with a Novel Range of Distortions
T2 - Pr3I3Ru), Y3I3Ru), and Y3I3Ir)
AU - Payne, Martin W.
AU - Dorhout, Peter K.
AU - Kim, Sung Jin
AU - Hughbanks, Timothy R.
AU - Corbett, John D.
PY - 1992
Y1 - 1992
N2 - The phases R3I3Ru (R = La, Pr, Gd, Y, Er) and R3I3Ir (R = Gd, Y) are obtained from the reactions of R, RI3, and Ru or Ir for 3-4 weeks in sealed Ta tubing at 850-975 °C, depending on the system. The title phases have been characterized by single-crystal X-ray means at room temperature, with space group P21/m and Z = 2 (Pr3I3Ru, Y3I3Ru, Y3I3Ir, respectively: a = 9.194 (1), 8.7001 (4), 8.6929 (7) Å; b = 4.2814 (5), 4.1845 (2), 4.2388 (4) Å; c = 12.282 (2), 12.1326 (6), 12.092 (2) Å; Å/² = 93.46 (1), 94.769 (5), 94.73 (1)°; R/Rw = 3.7/3.4, 3.2/5.5, 4.4/4.0%). The first phase contains quasi-infinite double chains of edge-sharing Pr6(Ru) octahedra that are sheathed and interbridged by iodine. An evidently continuous distortion of these chains parallels the a/b axial ratio (in the order listed in the first sentence) such that metal octahedra are no longer obvious in Y3I3Ir; rather chains of trans-edge-sharing square pyramidal Y4Ir units bonded base-to-base are more apt. Increased R-R, R-interstitial, and interstitial-interstitial bonding appears to parallel the degree of distortion. Magnetic data for La3I3Ru and Pr3I3Ru and the results of extended Hiickel band calculations on Pr3I3Ru are reported. Polar covalent Pr-Ru interactions and at least a quasi-closed shell configuration are emphasized by the latter.
AB - The phases R3I3Ru (R = La, Pr, Gd, Y, Er) and R3I3Ir (R = Gd, Y) are obtained from the reactions of R, RI3, and Ru or Ir for 3-4 weeks in sealed Ta tubing at 850-975 °C, depending on the system. The title phases have been characterized by single-crystal X-ray means at room temperature, with space group P21/m and Z = 2 (Pr3I3Ru, Y3I3Ru, Y3I3Ir, respectively: a = 9.194 (1), 8.7001 (4), 8.6929 (7) Å; b = 4.2814 (5), 4.1845 (2), 4.2388 (4) Å; c = 12.282 (2), 12.1326 (6), 12.092 (2) Å; Å/² = 93.46 (1), 94.769 (5), 94.73 (1)°; R/Rw = 3.7/3.4, 3.2/5.5, 4.4/4.0%). The first phase contains quasi-infinite double chains of edge-sharing Pr6(Ru) octahedra that are sheathed and interbridged by iodine. An evidently continuous distortion of these chains parallels the a/b axial ratio (in the order listed in the first sentence) such that metal octahedra are no longer obvious in Y3I3Ir; rather chains of trans-edge-sharing square pyramidal Y4Ir units bonded base-to-base are more apt. Increased R-R, R-interstitial, and interstitial-interstitial bonding appears to parallel the degree of distortion. Magnetic data for La3I3Ru and Pr3I3Ru and the results of extended Hiickel band calculations on Pr3I3Ru are reported. Polar covalent Pr-Ru interactions and at least a quasi-closed shell configuration are emphasized by the latter.
UR - http://www.scopus.com/inward/record.url?scp=33751390987&partnerID=8YFLogxK
U2 - 10.1021/ic00034a018
DO - 10.1021/ic00034a018
M3 - Article
AN - SCOPUS:33751390987
SN - 0020-1669
VL - 31
SP - 1389
EP - 1394
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 8
ER -