064 V-S-SR IC - Inorg. C hem. 1988, 27, 507-514 LMCT s tate...

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Inorg. Chem. 1988, 27, 507-514 507 LMCT state of [MoS412- and [WS412- is not much distorted with regard to the ground state while [Mn04]-, which photolyses ef- ficiently upon long-wavelength irradiati~n,~' is distorted much more ~trongly.~~~~~ Unfortunately, the excited-state distortions of [VS413- and [Res4]- are not known to establish a correlation between the extent of excited state distortion and the efficiency Acknowledgment. Financial support for this research by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie is gratefully acknowledged. Registry No. [MoS,I2-, 16330-92-0; [WS412-, 14916-78-0; [VS413-, 14791-51-6; [Res,]-, 16829-47-3; [~~0~~~12-, 16608-22-3; [wo2s212-, 16450-49-0; [vO2s2]3-, 26815-91-8; [Re02S2]-, 1121 13-55-0; 02, 7782- of the photoreaction. 44-7; S2, 23550-45-0; Sg, 10544-50-0. Contribution from the Department of Chemistry and the Molecular Structure Center, Indiana University, Bloomington, Indiana 47405 Metal/Sulfide/Thiolate Chemistry for an Early 3d Transition Metal: Variation of Product Identity as a Function of V:S Reaction Ratio and Structure and Redox Properties of Discrete V/S/edt Complexes Joanna K. Money, John C. Huffman, and George Christou*+ Received April 21, I987 A systematic investigation of the VCl,/elemental S/Na,edt reaction system in MeCN is described. Particular emphasis has been placed on determining the influence of the S:V ratio (n) on the identity of the reaction product(s). Values of n in the 0-2.5 range have been employed. In some cases, the influence of the edt2-:V ratio on reaction product(s) has also been investigated. These combined variations have led to the synthesis of five discrete complexes, the structures of two of which are described. The n = 0 reaction ratio leads to high-yield preparation of (PPh,),[V,(edt),] (1). The n = 0.5 reaction ratio yields a mixture of products, being composed of an approximately 3: 1 ratio of (NEt,),[V,(edt),] and (NEt4),[V3S4(edt),] (2). Complex 2 crystallizes in the monoclinic space group nl/n with the following unit cell dimensions at -154 OC: a = 14.168 (5) A, b = 18.446 (7) A, c = 19.803 (8) A, fl = 104.91 (2)O, and Z = 4. A total of 3806 unique reflections with F > 2.33a(F) were employed, and the structure solution was refined to values of conventional indices R and R, of 8.39 and 8.59%, respectively. The structure of the anion of 2 consists of a V, triangle with one central capping b3-S atom and a p-S atom bridging each edge. A terminal edt completes five-Coordination at each metal. The V3S, core can be described as a "partial cube" and is isostructural with the more common Mo3S4 cores in Mo/S chemistry. Charge considerations necessitate a mixed-valence trivanadium(III,2IV) description, but on the basis of inspection of structural parameters, there is no justification for a trapped-valence assignment, and the anion is best described as electronically delocalized with an average metal oxidation state of +32/3. The n = 1 reaction ratio yields (NEt,)Na[VS(edt),] (3), the structure of which had been determined in previous work and contains the multiply bonded VS2+ unit. The n = 1.5 reaction ratio gave differing products depending on the edt2-:V ratio employed. When edt2-:V = 3:1, high yields of 3 were obtained, whereas an edt2-:V =
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This note was uploaded on 01/15/2012 for the course CHM 2045 taught by Professor Mitchell during the Fall '07 term at University of Florida.

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064 V-S-SR IC - Inorg. C hem. 1988, 27, 507-514 LMCT s tate...

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