A New Class of Sulfido/Oxo(dithiolene)−Molybdenum(IV) Complexes Derived from Sulfido/Oxo-Bis(tetrasulfido)molybdenum(IV) Anions

Sugimoto, Hideki; Suyama, Koichiro; Sugimoto, Kunihisa; Takahashi, Isao; Hirota, Shun; Itoh, Shinobu

doi:10.1021/ic800832a

Cited by 12 publications

(15 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Taken together, these observations indicate that each Mo1 atom possesses a distorted square pyramidal geometry as commonly found in the Mo(IV) complexes, [MoS(didentate ligand) 2 ] 2− , (bidentate ligand = S 4 , 23 CS 4 , 31 L C4H8 , 18 S 2 C 2 Me 2 32 ), [MoS(bdt)(S 4 )] 2− , 33 and [MoS(bdtCl 2 )(S 4 )] 2− . 33 The Mo1 atom of MoSL COOMe also adopts a similar distorted square pyramidal geometry as MoSL Ph , and this is reflected by the S5-Mo1-S (L COOMe ) and S1-Mo1-S3 and S2-Mo1-S4 bond angles. With respect to the dimensions of L Ph and L COOMe , the four C-S bond lengths of L Ph (1.766(3) – 1.789(3) Å) and the three C-S bonds (1.748(6) – 1.774(4) Å), except for the C1-S1 bond (1.735(5) Å) of L COOMe , are in the typical range of C-S single bonds.…”

Section: Resultssupporting

confidence: 61%

Chalcogenidobis(ene-1,2-dithiolate)molybdenum(iv) complexes (chalcogenide E = O, S, Se): Probing MoE and ene-1,2-dithiolate substituent effects on geometric and electronic structure

et al. 2011

Self Cite

View full text Add to dashboard Cite

New square–pyramidal bis(ene–1,2–dithiolate)MoSe complexes, [MoIVSe(L)2]2−, have been synthesised along with their terminal sulfido analogues, [MoIVS(L)2]2−, using alkyl (LC4H8), phenyl (LPh) and methyl carboxylate (LCOOMe) substituted dithiolene ligands (LR). These complexes now complete three sets of MoIVO, MoIVS and MoIVSe species that are coordinated with identical ene–1,2–dithiolate ligands. The alkyl substituted [Mo(S/Se)(LC4H8)2]2 − complexes were reported in prior investigations (H. Sugimoto, T. Sakurai, H. Miyake, K. Tanaka and H. Tsukube, Inorg. Chem. 2005, 44, 6927, H. Tano, R. Tajima, H. Miyake, S. Itoh and H. Sugimoto, Inorg. Chem. 2008, 47, 7465). The new series of complexes enable a systematic investigation of terminal chalcogenido and supporting ene–1,2–dithiolate ligand effects on geometric structure, electronic structure, and spectroscopic properties. X–ray crystallographic analysis of these (Et4N)2[Mo(E)L2] (E = terminal chalcogenide) complexes reveals an isostructural Mo centre that adopts a distorted square pyramidal geometry. The M≡E bond distances observed in the crystal structures and the ν(M≡E) vibrational frequencies indicate that these bonds are weakened with an increase in L→Mo electron donation (LCOOMe < LPh < LC4H8), and this order is confirmed by an electrochemical study of the complexes. The 77Se NMR resonances in MoSeL complexes appear at lower magnetic fields as the selenido ion became less basic from MoSeLC4H8, MoSeLPh and MoSeLCOOMe. Electronic absorption and resonance Raman spectroscopies have been used to assign key ligand-field, MLCT, LMCT and intraligand CT bands in complexes that possess the LCOOMe ligand. The presence of low-energy intraligand CT transition in these MoELCOOMe compounds directly probes the electron withdrawing nature of the −COOMe substituents, and this underscores the complex electronic structure of square pyramidal bis(ene–1,2–dithiolate)-MoIV complexes that possess extended dithiolene conjugation.

show abstract

Section: Resultssupporting

confidence: 61%

Chalcogenidobis(ene-1,2-dithiolate)molybdenum(iv) complexes (chalcogenide E = O, S, Se): Probing MoE and ene-1,2-dithiolate substituent effects on geometric and electronic structure

et al. 2011

Self Cite

View full text Add to dashboard Cite

show abstract

“…(g) A synthetic Mo‐S compound with similar coordination environment, but coordinated by two polysulfide rings (George et al., ; Mcalpine et al., ). (h) Cuboid Fe‐Mo‐S cluster resembling the proposed structure of the FeMo cofactor in nitrogenase (Sugimoto et al., ). (i) Linear complex consisting of a 2 Fe‐2Mo cluster coordinated to MoS 4 2− , thought relevant for FeS assisted Mo removal in nature (Cramer et al., ; Helz et al., ; Venters et al., )…”

Section: Resultsmentioning

confidence: 99%

Evidence of molybdenum association with particulate organic matter under sulfidic conditions

et al. 2016

View full text Add to dashboard Cite

The geochemical behavior of molybdenum (Mo) in the oceans is closely linked to the presence of sulfide species in anoxic environments, where Fe availability may play a key role in the Mo scavenging. Here, we show that Mo(VI) is reduced in the presence of particulate organic matter (represented by sulfate-reducing bacteria). Molybdenum was immobilized at the surface of both living cells and dead/lysed cells, but not in cell-free control experiments. Experiments were carried out at four different Mo concentrations (0.1 to 2 mm) to yield cell-associated Mo precipitates with little or no Fe, consisting of mainly Mo(IV)-sulfide compounds with molecular structures similar to Mo enzymes and to those found in natural euxinic sediments. Therefore, we propose that Mo removal in natural sulfidic waters can proceed via a non-Fe-assisted pathway that requires particulate organic matter (dead or living sulfate-reducing bacteria). This pathway has implications for global marine Mo cycling and the current use of Mo-based proxies for paleo-environmental investigations.

show abstract

“…This complex was synthesized using the same procedure as 1 , 14 except (Et 4 N) 2 [MoO(S 4 )(bdtCl 2 )] (224 mg, 0.316 mmol) was used instead of (Et 4 N) 2 [MoO(S 4 )(bdt)]. Yield: 166 mg (67%).…”

Section: Synthesis and Characterization Of Complexesmentioning

confidence: 99%

“…11-13 Recently, we reported a Mo IV O complex which possesses both an ene–1,2–dithiolate ligand and an aromatic dithiolene ligand, (Et 4 N) 2 [Mo IV O(S 2 C 2 (CO 2 Me) 2 )(bdt)] ( 1 ) (Chart 1, S 2 C 2 (CO 2 Me) 2 = 1,2–dicarbomethoxyethylene–1,2– ditholate, bdt = 1,2–benzenedithiolate). 14 In contrast, Mo VI complexes with one or two ene–1,2–dithiolate ligands have been considered to be unstable for isolation as a result of autoredox reactions that may be facilitated by π–delocalization between the metal and ene–1,2–dithiolate ligands. 12, 15-18 Isolated Mo VI [Mo VI O 2 (ene-1,2-dithiolate) 2 ] 2− complexes are limited to [MoO 2 (mnt) 2 ] 2− (mnt = dicyanoethylene–1,2–dithiolate), 19 which is believed to be stabilized by the very strong electron withdrawing nature of the CN substituents.…”

Section: Introductionmentioning

confidence: 99%

Dioxomolybdenum(VI) Complexes with Ene-1,2-dithiolate Ligands: Synthesis, Spectroscopy, and Oxygen Atom Transfer Reactivity

et al. 2009

Self Cite

View full text Add to dashboard Cite

New dioxo–molybdenum(VI) complexes, (Et4N)(Ph4P)[MoVIO2(S2C2(CO2Me)2)(bdt)] (2) and (Et4N)(Ph4P)[MoVIO2(S2C2(CO2Me)2)(bdtCl2)] (4) (S2C2(CO2Me)2 = 1,2–dicarbomethoxyethylene–1,2–ditholate, bdt = 1,2–benzenedithiolate, bdtCl2 = 3,6–dichloro–1,2–benzenedithiolate), that possess at least one ene–1,2–dithiolate ligand were synthesized by the reaction of their mono–oxo–molybdenum(IV) derivatives, (Et4N)2[MoIVO(S2C2(CO2Me)2)(bdt)] (1) and (Et4N)2[MoIVO(S2C2(CO2Me)2)(bdtCl2)] (3), with Me3NO (Chart 1). Additionally, the bis(ene–1,2–dithiolate)MoVIO2 complex, (Et4N)(Ph4P)[MoVIO2(S2C2(CO2Me)2)2] (6), was isolated. Complexes 2, 4, and 6 were characterized by elemental analysis, negative–ion ESI mass spectrometry, and IR spectroscopy. X-ray analysis of 4 and 6 revealed a MoVI center that adopts a distorted octahedral geometry. Variable temperature 1H NMR spectra of (CD3)2CO solutions of the MoVIO2 complexes indicated that the Mo centers isomerize between Δ and Λ forms. The electronic structures of 2, 4, and 6 have been investigated by electronic absorption and resonance Raman spectroscopy and bonding calculations. The results indicate very similar electronic structures for the complexes and considerable π–delocalization between the MoVIO2 and ene–1,2–dithiolate units. The similar oxygen atom transfer kinetics for the complexes results from their similar electronic structures.

show abstract

A New Class of Sulfido/Oxo(dithiolene)−Molybdenum(IV) Complexes Derived from Sulfido/Oxo-Bis(tetrasulfido)molybdenum(IV) Anions

Cited by 12 publications

References 41 publications

Chalcogenidobis(ene-1,2-dithiolate)molybdenum(iv) complexes (chalcogenide E = O, S, Se): Probing MoE and ene-1,2-dithiolate substituent effects on geometric and electronic structure

Chalcogenidobis(ene-1,2-dithiolate)molybdenum(iv) complexes (chalcogenide E = O, S, Se): Probing MoE and ene-1,2-dithiolate substituent effects on geometric and electronic structure

Evidence of molybdenum association with particulate organic matter under sulfidic conditions

Dioxomolybdenum(VI) Complexes with Ene-1,2-dithiolate Ligands: Synthesis, Spectroscopy, and Oxygen Atom Transfer Reactivity

Contact Info

Product

Resources

About