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Synthesis, spectroscopy, and structural characterization of six-coordinate bis(aryldiazenido)rhenium and bis(diarylhydrazido)rhenium complexes. X-ray structures of (Et{sub 4}N)[Re(NNPh){sub 2}(O{sub 2}C{sub 6}H{sub 4}){sub 2}], (Et{sub 4}N)[Re(NNPh{sub 2}){sub 2}(O{sub 2}C{sub 6}H{sub 4}){sub 2}], and Na[Re(NNPh){sub 2}(O{sub 2}C{sub 6}H{sub 4}){sub 2}]{center_dot}CH{sub 3}CN

Journal Article · · Inorganic Chemistry

The reactions of the cis-dioxorhenium(VII)-catecholate complex [(CH{sub 3}CH{sub 2}){sub 4}N][ReO{sub 2}(O{sub 2}C{sub 6}H{sub 4}){sub 2}] (1) with either monosubstituted organohydrazines (C{sub 6}H{sub 5}NHNH{sub 2}; 4-BrC{sub 6}H{sub 4}NHNH{sub 2}) or 1,1 disubstituted organohydrazines (Ph{sub 2-}NNH{sub 2}) yield the cis-bis(diazenido) core complexes [(CH{sub 3}CH{sub 2}){sub 4}N][Re(NNR){sub 2}(O{sub 2}C{sub 6}H{sub 4}){sub 2}] (5, R = C{sub 6}H{sub 5}; 6, R = 4-BrC{sub 6}H{sub 4}) and the cis-bis(hydrazido) core species [(CH{sub 3}CH{sub 2}){sub 4}N][Re(NNPh{sub 2}){sub 2}(O{sub 2}C36H{sub 4}){sub 2}(O{sub 2}C36H{sub 4}){sub 2}] (7). Elution of 5 in a 3:1 mixture of toluene/methanol on a column of silica gel resulted in cation exchange to give Na[Re(NNPh){sub 2}-(O{sub 2}C{sub 6}H{sub 4}){sub 2}]{center_dot}CH{sub 3}CN (8) as a one-dimensional polymer ([Na(CH{sub 3}CN)]{sup +}[Re(NNPh){sub 2}(O{sub 2}C{sub 6}H{sub 4}){sub 2}]{sup {minus}}){sub 2}. Crystal data for C{sub 32}H{sub 38}N{sub 5}O{sub 4}Re (5): P2{sub 1}/c,a = 14.458(3) {angstrom}, b = 10.436(2) {angstrom}, c = 21.767(4) {angstrom}, {beta} = 107.04(3){degrees}, V = 3140(2) {angstrom}{sup 3}, Z = 4, D {sub calc} = 1.572 g cm{sup {minus}3}; structure solution and refinement based on 3256 reflections with I{sub o} {ge} 3{sigma}(I{sub o}) converged at R = 0.053. Crystal data for C{sub 44}H{sub 48}N{sub 5}O{sub 4}Re (7): P1, a = 11.660(2) {angstrom}, b = 11.864(2) {angstrom}, c = 15.400(2) {angstrom}, {alpha} = 107.12(3){degrees}, {beta} = 94.99(3){degrees}, {gamma} = 97.61(3){degrees}, V = 2000(1) {angstrom}{sup 3}, Z = 2, D{sub calc} = 1.490 g cm{sup {minus}3}; 3702 reflections, R = 0.0534. Crystal data for C{sub 26}H{sub 18}N{sub 5}NaO{sub 4}Re (8): P2/n, a = 5.785(1) {angstrom}, b = 9.670(2) {angstrom}, c = 23.142(5) {angstrom}. {beta} = 90.91(30)degrees, V = 1294.4(7) {angstrom}{sup 3}, Z = 2, D{sub calc} = 1.737 g cm{sup {minus}3}; 1517 reflections, R = 0.049.

Sponsoring Organization:
USDOE
DOE Contract Number:
FG02-93ER61571
OSTI ID:
421017
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 25 Vol. 33; ISSN 0020-1669; ISSN INOCAJ
Country of Publication:
United States
Language:
English