Structure of tetraphenylphosphonium (bipyridine)tetrachloromolybdate(III) [PPh4][MoCl4(bpy)]

Richards, Raymond L.; Shortman, Caroline; Povey, David C.; Smith, G. W.

doi:10.1107/s0108270187088899

Cited by 3 publications

(3 citation statements)

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“…The crystal structures of two members of this family, (PPha)MoC14(THF)2 (Hill, Leigh, Hutchinson & Zubieta, 1985) and (PPh4)-MoC14(bipy), bipy = bipyridine (Richards, Shortman, Povey & Smith, 1987), were published recently. The only structural information about the pyp+ cation comes from the crystal structure of pypHMoC15.H20 (BrenEiE, (~eh & Leban, 1988) where 1-(4-pyridyl)-pyridinium (pyp+) is protonated.…”

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confidence: 99%

Structure of 1-(4-pyridyl)pyridinium trans-tetrachlorodi(pyridine)molybdate(III)

Brenčíč¹,

Čeh²,

Leban³

1989

Acta Crystallogr C

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confidence: 99%

Structure of 1-(4-pyridyl)pyridinium trans-tetrachlorodi(pyridine)molybdate(III)

Brenčíč¹,

Čeh²,

Leban³

1989

Acta Crystallogr C

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“…Although this particular anion has previously been synthesized, the solvatochromic behavior it exhibits remains uninvestigated. In fact, different synthetic procedures have described the compound as purple, , red-orange, and dark red . To the best of our knowledge, there have been no reports of a Mo III complex possessing solvatochromism, especially with simple π-donating ligands such as Cl – .…”

Section: Resultsmentioning

confidence: 99%

“…Realizing that the 1,2-benzenedithiol acted as a reducing agent instead of a bidentate ligand as intended, we developed a new synthetic strategy to obtain these interesting complexes. A previous synthesis used Li 2 S 2 in a similar fashion to reduce [Mo(bpy)Cl 4 ], so lithium ethanethiolate (LiSEt) was chosen as a more convenient thiol-based reductant, similar to the bdt 2– that generated the [Li(bpy)][Mo III (bpy)Cl 4 ] complex (Figure a). LiSEt worked well in this capacity and, followed by salt metathesis with PPh 4 Br, produced the known complex [PPh 4 ][Mo(bpy)Cl 4 ] ( 1 ).…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Strongly Solvatochromic Molybdenum(III) Complexes

et al. 2019

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A series of seven molybdenum(III) complexes with the general formula of [Mo(diimine)Cl 4 ] − were synthesized and characterized by X-ray diffraction, IR, cyclic voltammetry (CV), and UV−vis. The complexes were discovered to be highly solvatochromic, showing shifts in λ max between ∼120 and 170 nm in solvents ranging from water to acetone. Varying the substituents on the diimine ligand influenced the absorption energy such that electron-withdrawing groups induced a red shift while electron-donating groups exhibited the opposite effect. The complexes were surprisingly stable in both acidic and basic solutions, and in the case where carboxylic acid substituents were present, additional shifts in the absorption maxima were observed, corresponding to the state of protonation of these groups. Both the Mo IV/III and Mo III/II redox couples were observed in CV experiments and were complemented with density functional theory (DFT) calculations.

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Element Misidentification in X-ray Crystallography: A Reassessment of the [MCl₂(diazadiene)] (M = Cr, Mo, W) Series

et al. 2013

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A series of reports describing the syntheses and structures of [MCl2(diazadiene)] (M = Cr, Mo, W) complexes is reassessed in the context of known chemistry of low-valent Group VI metal complexes, crystallographic trends such as M-Cl bond lengths and unit cell volumes, and calculated metal-ligand bond lengths. Crystallographic data and computational results are inconsistent with any of these species being second or third row transition metal complexes. A review of the crystallographic information files accompanying the [MCl2(diazadiene)] (M = Mo, W) published structures reveals that the metal atoms were inappropriately treated with partial site occupancy factors (0.775 for Mo; 0.4005 and 0.417 for W), the effect of which was to manifest lighter-element behavior and better refinement in accord with the metal atoms' correct identity. A deliberate synthesis and characterization by X-ray diffraction of [ZnCl2((Mes)dad(Me))] ((Mes)dad(Me) = 1,4-bis(2,4,6-trimethylphenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene) are reported. Refinement of this structure with the same combination of second or third row metal and offsetting partial site occupancy is shown to provide final refinement statistics essentially the same as with the correct model employing M = Zn at site occupancy 1.00. Use of the published method for synthesis of [WCl2(diazadiene)] with (Mes)dad(Me) and [WBr4(MeCN)2] in lieu of [WCl4(MeCN)2] is shown to produce [ZnBr2((Mes)dad(Me))], which has also been characterized by X-ray diffraction. It is concluded that the unusual putative 12-electron [MCl2(diazadiene)] (M = Cr, Mo, W) complexes are in all cases the corresponding [ZnCl2(diazadiene)] complexes, Zn having been commonly employed as reducing agent in their synthesis.

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Structure of tetraphenylphosphonium (bipyridine)tetrachloromolybdate(III) [PPh4][MoCl4(bpy)]

Cited by 3 publications

References 4 publications

Structure of 1-(4-pyridyl)pyridinium trans-tetrachlorodi(pyridine)molybdate(III)

Structure of 1-(4-pyridyl)pyridinium trans-tetrachlorodi(pyridine)molybdate(III)

Synthesis and Characterization of Strongly Solvatochromic Molybdenum(III) Complexes

Element Misidentification in X-ray Crystallography: A Reassessment of the [MCl₂(diazadiene)] (M = Cr, Mo, W) Series

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Structure of tetraphenylphosphonium (bipyridine)tetrachloromolybdate(III) [PPh4][MoCl4(bpy)]

Cited by 3 publications

References 4 publications

Structure of 1-(4-pyridyl)pyridinium trans-tetrachlorodi(pyridine)molybdate(III)

Structure of 1-(4-pyridyl)pyridinium trans-tetrachlorodi(pyridine)molybdate(III)

Synthesis and Characterization of Strongly Solvatochromic Molybdenum(III) Complexes

Element Misidentification in X-ray Crystallography: A Reassessment of the [MCl2(diazadiene)] (M = Cr, Mo, W) Series

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Element Misidentification in X-ray Crystallography: A Reassessment of the [MCl₂(diazadiene)] (M = Cr, Mo, W) Series