The tetrahydrofuran adduct Re2Br2(CO)(6)(THF)(2) reacts with 1,8-naphthalenedisulfide (NDS) to give Re2Br2(CO)(6)(NDS), which crystallizes in the monoclinic system, space group P2(1)/c, with cell constants a=10.071(4), b=21.229(5), c=10.135(7) Angstrom; beta=105.73(5)degrees, and Z=4 molecules per unit cell. The final R value is 0.044 for 2035 data (Mo-K-alpha). The Re2Br2(CO)(6) fragment is the same as in all previously determined structures of this series, having bridging bromides and a fac tricarbonyl arrangement about each rhenium atom. The rhenium atoms are also bridged by the disulfide fragment of NDS forming two five-membered rings of composition Re-S-S-Re-Br. The fold angle across the Br ... Br vector is 29 degrees. The Re-Br distances are unequal, with the shorter distances to the bromine closer to the naphthalene fragment; this bromine is further from the S-S bridge than the other. The Re-S and S-C distances average 2.48 and 1.78 Angstrom, respectively, while the S-S bond is 2.16 Angstrom long. Both the Re-S-S-Re and C-S-S-C torsion angles are nearly 0 degrees, which is a significant distinction from the previously investigated structures of this type. The NDS ligand is significantly non-planar, and this may be due to steric repulsion from the nearby carbonyl groups. The dibenzyldisulfide and dibenzyldiselenide complexes Re-2(mu-I)(2)(CO)(6)(E(2)Bz(2)), E=S, Se, have been prepared starting from the same THF rhenium(I) precursor. The Se NMR data of the dibenzyldiselenide complex show a downfield shift of about 165 ppm with respect to the uncomplexed molecule under the same conditions. Bis(dimethylphosphine)ethane gives ReI(CO)(3)(Me(2)PCH(2)CH(2)PMe(2)); iodide abstraction from the latter by silver triflate gave Re(SO3CF3)(CO)(3)(Me(2)PCH(2)CH(2)PMe(2)), which is suggested to contain the monodentate triflato ligand.

Synthesis of tricarbonyl derivatives of rhenium(I) with Group 16 donor atoms. Crystal and molecular structure of di-mu-bromo-mu-1,8-naphthalenedisulfide-bis(fac-tricarbonylrhenium(I))

CALDERAZZO, FAUSTO;MARCHETTI, FABIO;VITALI, DARIO
1996

Abstract

The tetrahydrofuran adduct Re2Br2(CO)(6)(THF)(2) reacts with 1,8-naphthalenedisulfide (NDS) to give Re2Br2(CO)(6)(NDS), which crystallizes in the monoclinic system, space group P2(1)/c, with cell constants a=10.071(4), b=21.229(5), c=10.135(7) Angstrom; beta=105.73(5)degrees, and Z=4 molecules per unit cell. The final R value is 0.044 for 2035 data (Mo-K-alpha). The Re2Br2(CO)(6) fragment is the same as in all previously determined structures of this series, having bridging bromides and a fac tricarbonyl arrangement about each rhenium atom. The rhenium atoms are also bridged by the disulfide fragment of NDS forming two five-membered rings of composition Re-S-S-Re-Br. The fold angle across the Br ... Br vector is 29 degrees. The Re-Br distances are unequal, with the shorter distances to the bromine closer to the naphthalene fragment; this bromine is further from the S-S bridge than the other. The Re-S and S-C distances average 2.48 and 1.78 Angstrom, respectively, while the S-S bond is 2.16 Angstrom long. Both the Re-S-S-Re and C-S-S-C torsion angles are nearly 0 degrees, which is a significant distinction from the previously investigated structures of this type. The NDS ligand is significantly non-planar, and this may be due to steric repulsion from the nearby carbonyl groups. The dibenzyldisulfide and dibenzyldiselenide complexes Re-2(mu-I)(2)(CO)(6)(E(2)Bz(2)), E=S, Se, have been prepared starting from the same THF rhenium(I) precursor. The Se NMR data of the dibenzyldiselenide complex show a downfield shift of about 165 ppm with respect to the uncomplexed molecule under the same conditions. Bis(dimethylphosphine)ethane gives ReI(CO)(3)(Me(2)PCH(2)CH(2)PMe(2)); iodide abstraction from the latter by silver triflate gave Re(SO3CF3)(CO)(3)(Me(2)PCH(2)CH(2)PMe(2)), which is suggested to contain the monodentate triflato ligand.
W., Baratta; I., Bernal; Calderazzo, Fausto; J. D., Korp; L. S., Magill; Marchetti, Fabio; Vitali, Dario
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11568/204808
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