Dithiolene transfer from nickel to a dimolybdenum centre: the first dithiolene alkyne complex

Adams, Harry; Morris, Michael J.; Morris, Sarah A.; Motley, Jeffrey C

doi:10.1016/j.jorganchem.2003.10.041

Cited by 15 publications

(18 citation statements)

References 44 publications

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“…4 N][16], which was fully flushed from the column with 100% CH 3 CN. The solvent was removed from the eluant in vacuo, and the residue was washed with Et 2 O (3 × 10 mL).…”

supporting

confidence: 73%

“…These molecules have been of considerable usefulness as entry points toward small-molecule analogues of the catalytic sites of molybdo- and tungstoenzymes . Others, − particularly Morris and co-workers, − have effectively exploited this behavior for the preparation of a variety of new organometallic and inorganic transition-metal complexes. In these examples, the value-added product is the coordination complex formed by oxidative addition of the dithiolene ligand, while [(R 2 C 2 S 2 )M] x is separated as an oligomeric or insoluble polymeric byproduct.…”

Section: Introductionmentioning

confidence: 99%

“…1.73 (m, 8H, Cy), 1.54−1.46 (m, 8H, Cy) 13. C NMR (δ, ppm in CD 2 Cl 2 ): 142.4, 138.4, 135.9 (t), 130.1, 127.9, 126.3, 55 4. (Cy, CH), 32.4 (Cy, CH 2 ), 25.2 (Cy, CH 2 ), 22.9 (Cy, CH 2 ).…”

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confidence: 99%

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Group 10 Metal Dithiolene Bis(isonitrile) Complexes: Synthesis, Structures, Properties, and Reactivity

et al. 2020

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Reaction of [(Ph2C2S2)2M] (M = Ni 2+ , Pd 2+ , Pt 2+ ) with 2 eq of RN≡C (R = Me (a), Bn (b), Cy (c), t Bu (d), 1-Ad (e), Ph (f)) yields [(Ph2C2S2)M(C≡NR)2] (M= Ni 2+ , 4a-4f; M = Pd 2+ , 5a-5f; M = Pt 2+ , 6a-6f), which are air-stable and amenable to chromatographic purification. All members have been characterized crystallographically. Structurally, progressively greater planarity tends to be manifest as M varies from Ni to Pt, and a modest decrease in the C≡N bond length of coordinated C≡NR appears in moving from Ni toward Pt. Vibrational spectroscopy (CH2Cl2 solution) reveals νC≡N frequencies for [(Ph2C2S2)M(C≡NR)2] that are substantially higher than for free C≡NR and increase as M ranges from Ni to Pt. This trend is interpreted as arising from increasing positive charge at M that stabilizes the linear, charge-separated resonance form of the ligand over the bent form with lowered C-N bond order. UV-vis spectra reveal lowest energy transitions that are assigned as HOMO (dithiolene π) → LUMO (M-L σ*) excitations. Oneelectron oxidations of [(Ph2C2S2)M(C≡NR)2] are observed at ~+0.5 V due to Ph2C2S2 2-→ Ph2C2S -S • + e -. Chemical oxidation of [(Ph2C2S2)Pt(C≡N t Bu)2] with [(Br-p-C6H4)3N][SbCl6] yields [(Ph2C2S -S • )Pt(C≡N t Bu)2] 1+ , identified spectroscopically, but in the crystalline state [[(Ph2C2S -S • )Pt(C≡N t Bu)2]2] 2+ prevails, which forms via axial Pt•••S interactions and pyramidalization at metal. Complete substitution of MeNC from [(Ph2C2S2)Ni(C≡NMe)2] by 2,6-Me2py under forcing conditions yields [(2,6-Me2py)Ni(μ2-η 1 ,η 1 -S',η 1 -S"-C2Ph2)]2 (8), which features a folded Ni2S2 core. In most cases, isonitrile substitution from [(Ph2C2S2)M(C≡NMe)2] with monodentate ligands (L = phosphine, CN -, carbene) typically leads to [(Ph2C2S2)M(L)(C≡NMe)] n (n = 0 or 1 -), wherein νC≡N varies according to the relative σ donating power of L (9 -21). Use of 1,3-bis(2,6diisopropylphenyl)imidazol-2-ylidene (IPr) provides [(Ph2C2S2)M(IPr)(C≡NMe)] for M = Ni (18)or Pd ( 19), but for Pt , attack by IPr at the isonitrile carbon occurs to yield the unusual η 1 ,κCketenimine complex [(Ph2C2S2)Pt(C(NMe)(IPr))(C≡NMe)] (20).

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“…4 N][16], which was fully flushed from the column with 100% CH 3 CN. The solvent was removed from the eluant in vacuo, and the residue was washed with Et 2 O (3 × 10 mL).…”

supporting

confidence: 73%

Section: Introductionmentioning

confidence: 99%

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Group 10 Metal Dithiolene Bis(isonitrile) Complexes: Synthesis, Structures, Properties, and Reactivity

et al. 2020

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“…75,76 The reaction of [Ni(S 2 C 2 Ph 2 ) 2 ] with nickelocene to give [CpNi-(S 2 C 2 Ph 2 )] also produced complex 2, and in this case, an ion was observed in the mass spectrum at m/z 1806, indicating a hexameric structure. 77 We have previously observed its formation in reactions of [Ni(S 2 C 2 Ph 2 ) 2 ] with carbonylcontaining substrates, 55 though interestingly, in other cases involving dithiolene transfer to complexes containing halides (such as [CpMo(CO) 3 Cl] or [RuCl 2 (PPh 3 ) 3 ]), it was not produced, and the fate of the nickel in these reactions remains unclear. 56,57 Bis-or trisdithiolene complexes of the general formula [M(S 2 C 2 R 2 ) 2 ] or [M(S 2 C 2 R 2 ) 3 ] are relatively common and can be prepared for most of the transition metals.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis of Mono- and Diiron Dithiolene Complexes as Hydrogenase Models by Dithiolene Transfer Reactions, Including the Crystal Structure of [{Ni(S₂C₂Ph₂)}₆]

et al. 2019

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The dithiolene transfer reaction between the nickel bis(dithiolene) complex [Ni(S 2 C 2 Ph 2) 2 ] and iron carbonyls has been reinvestigated and the conditions for the production of the dinuclear product [Fe 2 (µ-S 2 C 2 Ph 2)(CO) 6 ] have been optimised. Interception of a purple intermediate, thought to be [Fe(CO) 3 (S 2 C 2 Ph 2)], in the reaction of [Fe(CO) 5 ] with [Ni(S 2 C 2 Ph 2) 2 ] by the addition of PPh 3 affords the new dark blue mononuclear complex [Fe(CO) 2 (PPh 3)(S 2 C 2 Ph 2)] in good yield. The fate of the nickel dithiolene fragments in these reactions has also been established by crystallographic characterisation of the hexamer [{Ni(S 2 C 2 Ph 2)} 6 ] and the trinuclear cluster [Ni 3 (µ-S 2 C 2 Ph 2) 3 (PPh 3) 2 ]. The substitution reactions of [Fe 2 (µ-S 2 C 2 Ph 2)(CO) 6 ] with PPh 3 in the presence of Me 3 NO to give monosubstituted [Fe 2 (µ-S 2 C 2 Ph 2)(CO) 5 (PPh 3)] and disubstituted [Fe 2 (µ-S 2 C 2 Ph 2)(CO) 4 (PPh 3) 2 ] are also reported.

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“…In recent years we have been examining the synthesis of both new and known dithiolene complexes by the intermetallic transfer of the dithiolene ligand, usually from the readily prepared nickel complex [Ni(S2C2Ph2)2] to metal centres including molybdenum, tungsten, iron and page 4 ruthenium [18][19][20][21]. In the current instance we were drawn to investigate complexes with nitrosyl co-ligands firstly because the NO ligand, like the dithiolene, is a non-innocent variable electron donor ligand; it is also of current interest as a biological signalling molecule.…”

Section: Introductionmentioning

confidence: 99%

Dithiolene transfer to the molybdenum nitrosyl complex [CpMo(CO)2(NO)]: Formation of bimetallic complexes

Adams

Grimes

Morris

et al. 2018

Journal of Organometallic Chemistry

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The nitrosyl complex [CpMo(CO)2(NO)] (Cp = -C5H5) reacts with the nickel dithiolene complex [Ni(S2C2Ph2)2] to give the expected dimolybdenum complex [Mo2(NO)2(-S2C2Ph2)2Cp2], but the major product consists of two separable isomers of the tetranuclear complex [Mo2Ni2(NO)2(-S2C2Ph2)4Cp2], which comprises two CpMo(NO)Ni(S2C2Ph2)2 units joined through bridging sulfur atoms. page 3 Abstract The reaction of the nitrosyl complex [CpMo(CO)2(NO)] (Cp = -C5H5) with the nickel dithiolene complex [Ni(S2C2Ph2)2] produces the expected dimolybdenum complex [Mo2(NO)2(-S2C2Ph2)2Cp2], but only as a minor product (13% yield). The major product (41%) consists of two separable isomers of the tetranuclear complex [Mo2Ni2(NO)2(-S2C2Ph2)4Cp2], which comprises two CpMo(NO)Ni(S2C2Ph2)2 units joined through bridging sulfur atoms. The isomers differ in the orientation of one dimeric unit in relation to the other. All three compounds have been structurally characterised.

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Dithiolene transfer from nickel to a dimolybdenum centre: the first dithiolene alkyne complex

Cited by 15 publications

References 44 publications

Group 10 Metal Dithiolene Bis(isonitrile) Complexes: Synthesis, Structures, Properties, and Reactivity

Group 10 Metal Dithiolene Bis(isonitrile) Complexes: Synthesis, Structures, Properties, and Reactivity

Synthesis of Mono- and Diiron Dithiolene Complexes as Hydrogenase Models by Dithiolene Transfer Reactions, Including the Crystal Structure of [{Ni(S₂C₂Ph₂)}₆]

Dithiolene transfer to the molybdenum nitrosyl complex [CpMo(CO)2(NO)]: Formation of bimetallic complexes

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Dithiolene transfer from nickel to a dimolybdenum centre: the first dithiolene alkyne complex

Cited by 15 publications

References 44 publications

Group 10 Metal Dithiolene Bis(isonitrile) Complexes: Synthesis, Structures, Properties, and Reactivity

Group 10 Metal Dithiolene Bis(isonitrile) Complexes: Synthesis, Structures, Properties, and Reactivity

Synthesis of Mono- and Diiron Dithiolene Complexes as Hydrogenase Models by Dithiolene Transfer Reactions, Including the Crystal Structure of [{Ni(S2C2Ph2)}6]

Dithiolene transfer to the molybdenum nitrosyl complex [CpMo(CO)2(NO)]: Formation of bimetallic complexes

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Synthesis of Mono- and Diiron Dithiolene Complexes as Hydrogenase Models by Dithiolene Transfer Reactions, Including the Crystal Structure of [{Ni(S₂C₂Ph₂)}₆]