The molybdenum:sulfur bond distance in di-.mu.-sulfido-bis[sulfido(N,N-diethyldithiocarbamato)molybdenum(V)]

Huneke, James T.; Enemark, John H.

doi:10.1021/ic50190a073

Cited by 37 publications

(14 citation statements)

References 14 publications

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“…In addition, the resulting 16e Cp*Mo(NO)(κ 1 -dmpeS) fragment is linked to another of its kind by a MoSMo bridge that allows each metal center to attain the favored 18e configuration . The molybdenum–sulfur bond length of 2.2965(4) Å is intermediate between those reported for MoS (∼2.10–2.20 Å) and Mo–S (∼2.35–2.45 Å) linkages, − and there is no Mo–Mo bond because the separation of 4.4559(10) Å precludes a significant interaction between the metal centers. , In addition, the PS distance of 1.9647(12) Å is as expected for such a bond . In the solid state, the two halves of 3 are crystallographically equivalent, and the molecule belongs to the C 2 point group (Figure ).…”

Section: Results and Discussionmentioning

confidence: 97%

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ²-dmpe)

et al. 2017

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Reaction of Cp*Mo(NO)Cl with 1 equiv of 1,2-bis(dimethylphosphino)ethane (dmpe) in THF at ambient temperature forms [Cp*Mo(NO)(Cl)(κ-dmpe)]Cl (1), which is isolable as an analytically pure yellow powder in 65% yield. Further addition of 2 equiv of CpCo to 1 in CHCl affords dark red Cp*Mo(NO)(κ-dmpe) (2), which was isolated in 36% yield by recrystallization from EtO at -30 °C. Reaction of a benzene solution of 2 with an equimolar amount of elemental sulfur results in the immediate production of dark blue (μ-S)[Cp*Mo(NO)(κ-dmpeS)] (3), which is a rare example of a bimetallic transition-metal complex bridged by only a single sulfur atom and involving Mo═S═Mo bonding. In contrast, reaction of 2 with an excess of sulfur in benzene results in the formation of Cp*Mo(NO)(η-S)(κ-dmpeS) (4). Complex 4 can also be formed by the addition of elemental sulfur to 3, thereby indicating that 3 is a precursor to 4. Cp*Mo(NO)(κ-dmpe) (2) also undergoes interesting transformations when treated with organic bromides. For instance, reaction of 2 with 5 equiv benzyl bromide in THF produces the bimetallic complex (μ-dmpe)[Cp*Mo(NO)Br] (5) and bibenzyl after 4 d at 70 °C probably via radical intermediates. In contrast to its reaction with benzyl bromide, complex 2 forms [Mo(NO)Br(κ-dmpe)] (6), olefin, alkane, and Cp*H when treated with 5 equiv of 1-bromopropane or 1-bromooctane in THF at 70 °C for 72 h. Interestingly, complex 2 does not display any reactivity with bromobenzene or 1-bromoadamantane even after being heated for several days at 70 °C. All new complexes were characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them were established by single-crystal X-ray crystallographic analyses.

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Section: Results and Discussionmentioning

confidence: 97%

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ²-dmpe)

et al. 2017

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“…of the active enzyme provides clear evidence for a sulphur atom about 0.225 nm from molybdenum. Such a distance is relatively long for a terminal sulphur ligand of molybdenum, typical values for such a bond ranging from 0.21 nm (Huneke & Enemark, 1978) to 0.22nm (Diemann & Muller, 1973). Nevertheless, the observed bond length is far shorter than could reasonably be expected for a molybdenum(VI)cysteinyl or -persulphide sulphur, for both of which the shortest approach is about 0.24 nm (Stiefel, 1977;Muller et al, 1979).…”

Section: Structure and Mechanism Of Action Of Xanthine Oxidasementioning

confidence: 99%

X-ray absorption spectroscopy of xanthine oxidase. The molybdenum centres of the functional and the desulpho forms

Bordas¹,

Bray²,

Garner³

et al. 1980

Biochemical Journal

132

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X-ray absorption spectra have been recorded for the molybdenum K-edge region of xanthine oxidase. Both the absorption edge and the extended fine structure (e.x.a.f.s.) regions were investigated. Spectra were obtained for samples of the desulpho enzyme as well as for mixtures of this with the active enzyme. The spectrum of the pure active form was then obtained by difference. The desulpho enzyme shows a pronounced step in the absorption edge, of a type previously associated terminal oxygen ligands. In the active enzyme this step has decreased markedly. Satisfactory simulations of the e.x.a.f.s. spectrum of the desulpho enzyme could be obtained by assuming the molybdenum to be bonded to two terminal oxygen atoms (Mo = O about .175 nm), two sulphur atoms (presumably from cysteine residues, Mo-S about .0250 nm) and one sulphur atom (presumably from a methionine residue, Mo-S about 0.290 nm). E.x.a.f.s. of the active enzyme differed appreciably from this. In keeping with earlier proposals [Gutteridge, Tanner & Bray (1978) Biochem. J. 175, 887-897], the spectrum of the active enzyme could be simulated if a sulphur atom at about 0.225 nm (i.e. presumably a terminal sulphur atom) replaced one of the terminal oxygen atoms of the desulpho from, with small changes in the other bond distances. Validity of the interpretative procedures, which involved phase shift and amplitude calculations ab initio, was demonstrated by using low molecular weight compounds of known structure.

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“…The elemental analysis of 1 or 2 is consistent with their chemical formula. In the IR spectra of 1 and 2, characteristic bands due to Mo Ä/S (540 cm (1 ) and Mo 2 (m-S) 2 (450 cm (1 ) vibrations of the precursor [(dtc) 2 Mo 2 S 2 (m-S) 2 ] [42] are replaced by a medium strength band at 517 cm (1 (1) or 518 cm (1 (2) and a weaker band at 465 cm (1 (1) or 480 cm (1 (2). The 1 H-NMR spectrum of 1 in CDCl 3 at room temperature showed a doublet of doublet for methyl groups at 0.98 ppm and a multiplet for methylene groups at 2.83 Á/2.96 ppm, while that of 2 exhibited a quadruplet and triplet related to CH 2 and CH 3 protons at 2.96 and 0.90 ppm.…”

Section: Preparations Of 1 Andmentioning

confidence: 99%

“…[(dtc) 2 Mo 2 S 2 (m-S) 2 ] was prepared according to the literature method [42]. Other chemicals were obtained from commercial sources and used as received.…”

Section: Generalmentioning

confidence: 99%

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Stepwise addition of CuBr at [(dtc)2Mo2(S)2(μ-S)2] (dtc=diethyldithiocarbamate): syntheses and crystal structures of two Mo/Cu/S clusters [(dtc)2Mo2(μ3-S)(μ-S)3(CuBr)] and [(dtc)2Mo2(μ3-S)4(CuBr)2]

Wei

et al. 2003

Journal of Organometallic Chemistry

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The molybdenum:sulfur bond distance in di-.mu.-sulfido-bis[sulfido(N,N-diethyldithiocarbamato)molybdenum(V)]

Cited by 37 publications

References 14 publications

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ²-dmpe)

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ²-dmpe)

X-ray absorption spectroscopy of xanthine oxidase. The molybdenum centres of the functional and the desulpho forms

Stepwise addition of CuBr at [(dtc)2Mo2(S)2(μ-S)2] (dtc=diethyldithiocarbamate): syntheses and crystal structures of two Mo/Cu/S clusters [(dtc)2Mo2(μ3-S)(μ-S)3(CuBr)] and [(dtc)2Mo2(μ3-S)4(CuBr)2]

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The molybdenum:sulfur bond distance in di-.mu.-sulfido-bis[sulfido(N,N-diethyldithiocarbamato)molybdenum(V)]

Cited by 37 publications

References 14 publications

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ2-dmpe)

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ2-dmpe)

X-ray absorption spectroscopy of xanthine oxidase. The molybdenum centres of the functional and the desulpho forms

Stepwise addition of CuBr at [(dtc)2Mo2(S)2(μ-S)2] (dtc=diethyldithiocarbamate): syntheses and crystal structures of two Mo/Cu/S clusters [(dtc)2Mo2(μ3-S)(μ-S)3(CuBr)] and [(dtc)2Mo2(μ3-S)4(CuBr)2]

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Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ²-dmpe)

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ²-dmpe)