719296-75-0

Upstream product

• 75675-64-8 {CpMo(μ-S)(μ-SH)}2 
• 100-53-8 phenylmethanethiol 
• 102-04-5 1,3-Diphenylpropanone 
• 727721-79-1 [CpMo(CO)(μ-SBz)]2(μ-S) 
• 6493-73-8 dibenzyltrisulfide 
• 150-60-7 dibenzyl disulphide 

Relevant academic research and scientific papers

Isolation and characterization of thiolato complexes of [CpCr(SBz)]2S, isomeric trans [CpMo(CO)(SBz)]2 and [CpMo(SBz)2]2 (Cp = (η5-C5H5), Bz = PhCH2–) from the reactivity of bibenzyl disulfide towards [CpM(CO)3]2 (M = Cr, Mo)

The reactions of [CpM(CO)3]2 (M = Cr (1), Mo (3)) with Bz2S2 have been investigated. 1 underwent a facile reaction at ambient temperature which led to the isolation of [CpCr(CO)2]S (5), [CpCr(CO)2(SBz)]2 (6) and [CpCr(SBz)]2S (7) in 28.8, 42.6 and 11.8% yield, respectively. A similar reaction at 110 °C with its congener, [CpCr(CO)2]2 (Cr[tbnd]Cr) (2) yielded only thermolytic products of 5 (40.3%) and Cp4Cr4S4 (8) (10.6%). With the Mo analogue 3, only the decarbonylated [CpMo(CO)2]2 (Mo[tbnd]Mo) (4) reacts at 70 °C to give an isomeric pair of trans syn and anti [CpMo(CO)(SBz)]2 (9a & 9b), [CpMo(SBz)(S)]2 (10) and [CpMo(CO)(SBz)]2S (11) in 43.3, 34.1, 5.5 and 3.1% yield, respectively. A totally decarbonylated new complex of [CpMo(SBz)2]2 (12) was obtained in 33.2% yield from the co-thermolysis of Bz2S2 with 9a at 110 °C. All products were fully characterized with NMR and IR spectroscopy and C, H analysis. The molecular structures of 7, 9b and 12 have been elucidated by single crystal X-ray diffraction. Plausible mechanistic pathways leading to the formation of 7, 9 and 12 were discussed.

Desulfurization of bibenzyl trisulfide by [CpMo(CO)3]2: Formation and isolation of thiolato-bridged dimolybdenum complexes of [CpMo(CO)2(SBz)]2, [CpMo(CO)(SBz)]2S and [CpMo(SBz)S]2 (Cp = (η5-C5H5), Bz = PhCH2-). Crystal structures of two polymorphs of [CpMo(SBz)S]2

The reaction of [CpMo(CO)3]2 (1) with a molar equivalent of Bz2S3 at 60 °C for 3.5 h has led to the isolation of [CpMo(CO)2(SBz)]2 (2), [CpMo(CO)(SBz)]2S (3) and [CpMo(SBz)S]2 (4) in 16.9%, 3.1% and 61.1% yields, respectively, as main products. Thermolytic studies showed that 2 underwent stepwise decarbonylation to give 3 and 4. All the three products of 2, 3 and 4 were thiolato-bridged dimolybdenum complexes with bond orders of zero, one and two for 2, 3 and 4, respectively. In addition, both 3 and 4 have one and two S atoms bridged in a μ-η2-mode, respectively. The structures of 2 and 3 have been reported previously. The totally decarbonylated 4 was isolated as polymorphs, 4a and 4b, which have been characterized by elemental, spectral analyses and structurally determined.

Activation of the sulfhydryl group by Mo centers: Kinetics of reaction of benzyl radical with a binuclear Mo(μ-SH)Mo complex and with arene and alkane thiols

This paper provides evidence from kinetic experiments and electronic structure calculations of a significantly reduced S-H bond strength in the Mo(μ-SH)Mo function in the homogeneous catalyst model, CpMo(μ-S) 2(μ-SH)2MoCp (1, Cp = η 5-cyclopentadienyl). The reactivity of 1 was explored by determination of a rate expression for hydrogen atom abstraction by benzyl radical from 1 (log(kabs/M-1 s-1) = (9.07 ± 0.38) - (3.62 ± 0.58)/θ) for comparison with expressions for CH3(CH2)7SH, log(kabs/M -1 s-1) = (7.88 ± 0.35) - (4.64 ± 0.54)/θ, and for 2-mercaptonaphthalene, log(kabs/M -1 s-1) = (8.21 ± 0.17) - (4.24 ± 0.26)/θ (θ = 2.303RT kcal/mol, 2σ error). The rate constant for hydrogen atom abstraction at 298 K by benzyl radical from 1 is 2 orders of magnitude greater than that from 1-octanethiol, resulting from the predicted (DFT) S-H bond strength of 1 of 73 kcal/mol. The radical CpMo(μ-S) 3(μ-SH)MoCp, 2, is revealed, from the properties of slow self-reaction, and exclusive cross-combination with reactive benzyl radical, to be a persistent free radical.