Synthesis, characterization, and molecular structure of the new S{sub 2}O complex Mo(S{sub 2}O)(S{sub 2}CNEt{sub 2}){sub 3}{lg_bullet}1/2Et{sub 2}O
- Indiana Univ., Bloomington, IN (United States)
The reaction of [Mo(S{sub 2})(S{sub 2}CNEt{sub 2}){sub 3}](1) with 1 equiv of meta-chloroperbenzoic acid (mCPBA) in CH{sub 2}Cl{sub 2} at 0 {degrees}C yields [Mo(S{sub 2}O)(S{sub 2}CNEt{sub 2}){sub 3}] (2) in {approximately} 70% yield. Complex 2 crystallizes from MeNO{sub 2}/Et{sub 2}O as the hemiether solvate in the monoclinic space group C2/c with the following unit cell dimensions at -165 {degrees}C: a = 18.294(4) {Angstrom}, b = 9.468(2) {Angstrom}, c = 32.101(7) {Angstrom}, {beta} + 92.75(1){degrees}, and Z=8. A total of 2641 unique data with F>2.33{sigma}(F) were refined to values of R and R{sub w} of 3.99 and 3.89%, respectively. The structure of 2{lg_bullet}{sup 1}/{sub 2}EtO shows a distorted pentagonal bipyramidal Mo center, with the S{sub 2}O ligand coordinated to an axial site in an asymmetric {eta}{sup 2}-S,S{prime}-fashion. The EPR and electronic spectra and electrochemical properties of 1 and 2 are very similar: for 1, =1.977,=38G, and E{sup 1}/{sub 2} = -0.23 and -1.44 V vs Fc/Fc{sup +} in CH{sub 2}Cl{sub 2}/0.5 M Bu{sub 4}{sup n}NPF{sub 6}; for 2, = 1.982, = 39 G, and E{sup 1}/{sub 2} = -0.04 and -1.62 V. All the aforementioned electrochemical processes are quasi-reversible at 25 {degrees}C, bulk controlled potential electrolyses affording mixtures of products in all cases. Ferrocenium oxidation of 1 in the presence or absence of H{sub 2}O affords salts containing the known ions [MoO(S{sub 2}CNEt{sub 2}){sub 3}]{sup +} and [Mo(S{sub 2}CNEt{sub 2}){sub 4}]{sup +}, respectively. Extended Hueckel MO calculations show that S{sub 2}O is both a weaker {pi}-acid and {pi}-base than S{sub 2} in this system and that the electronic structures of 1 and 2 are similar, in agreement with experimental observation, leading to the conclusion that 2 is best considered as a Mo{sup V} complex bearing an (S{sub 2}O){sup 2{minus}} ligand.
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- FG02-87ER13702
- OSTI ID:
- 420964
- Journal Information:
- Inorganic Chemistry, Vol. 33, Issue 17; Other Information: PBD: 17 Aug 1994
- Country of Publication:
- United States
- Language:
- English
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