Some mercaptides and mercaptide complexes of nickel and palladium

Hayter, R. G.; Humiec, F.

doi:10.1016/0022-1902(64)80326-2

Cited by 60 publications

(16 citation statements)

References 9 publications

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“…Solvents were HPLC-grade and dried by filtration through activated alumina or distilled under nitrogen over an appropriate drying agent. Ni(pdt)(dppe), 35 Ni(SPh) 2 (dppe), 36 Ni(SPh) 2 (dmpe), 16 NiCl 2 (dppbz), 37 NiCl 2 (dcpe), 38 NiCl 2 (dppf), 39 NiCl 2 (dppp), 40 and 1 12 were prepared according to modified literature procedures. Chromatography was conducted with Siliaflash® P60 from Silicycle (230-400 mesh).…”

Section: Methodsmentioning

confidence: 99%

Active-Site Models for the Nickel–Iron Hydrogenases: Effects of Ligands on Reactivity and Catalytic Properties

et al. 2011

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Described are new derivatives of the type [HNiFe(SR)2(diphosphine)(CO)3]+, which feature a Ni(diphosphine) group linked to a Fe(CO)3 group via two bridging thiolate ligands. Previous work had described [HNiFe(pdt)(dppe)(CO)3]+ ([1H]+) and its activity as a catalyst for the reduction of protons. Work described in this paper focused on the effects of the diphosphine attached to nickel as well as the dithiolate bridge, 1,3-propanedithiolate (pdt) vs 1,2-ethanedithiolate (edt). A new synthetic route to these Ni-Fe dithiolates is described, involving reaction of Ni(SR)2(diphosphine) with FeI2(CO)4 followed by in situ reduction with cobaltocene. Evidence is presented that this route proceeds via metastable μ-iodo derivatives. Attempted isolation of such species led to the crystallization of NiFe(Me2pdt)(dppe)I2, which features tetrahedral Fe(II) and square planar Ni(II) centers (Me2pdt = 2,2-dimethylpropanedithiol). The new tricarbonyls prepared in this work are NiFe(pdt)(dcpe)(CO)3 (2, dcpe = 1,2-bis(dicyclohexylphosphino)ethane), NiFe(edt)(dppe)(CO)3 (3), and NiFe(edt)(dcpe)(CO)3 (4). Attempted preparation of a phenylthiolate-bridged complex via the FeI2(CO)4 + Ni(SPh)2(dppe) route gave the tetrametallic species [(CO)2Fe(SPh)2Ni(CO)]2(μ-dppe)2. Crystallographic analysis of the edt-dcpe compund [2H]BF4 and the edt-dppe compound [3H]BF4 verified their close resemblance. Each features pseudo-octahedral Fe and square pyramidal Ni centers. Starting from [4H]BF4 we prepared the PPh3 derivative [HNiFe(edt)(dppe)(PPh3)(CO)2]BF4 ([5H]BF4), which was obtained as a ~2:1 mixture of unsymmetrical and symmetrical isomers. Acid-base measurements indicate that changing from Ni(dppe) to Ni(dcpe) decreases the acidity of the cationic hydride complexes by 2.5 pKaMeCN units, from ~11 to ~13.5 (previous work showed that substitution at Fe leads to more dramatic effects). The redox potentials are more strongly affected by the change from dppe to dcpe, for example the [2]0/+ couple occurs at E1/2 = −820 for [2]0/+ vs −574 mV (vs Fc+/0) for [1]0/+. Changes in the dithiolate do not affect the acidity or the reduction potentials of the hydrides. The acid-independent rate of reduction of CH2ClCO2H by [2H]+ is ca. 50 s−1 (25 °C), twice that of [1H]+. The edt-dppe complex [2H]+ proved to be the most active catalyst, with an acid-independent rate of 300 s−1.

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Section: Methodsmentioning

confidence: 99%

Active-Site Models for the Nickel–Iron Hydrogenases: Effects of Ligands on Reactivity and Catalytic Properties

et al. 2011

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“…[34] reported in the literature [16] [26] . The NiϪS and PdϪS dis-and [M(SAr) 2 (dppe)] (M ϭ Pd, Pt) [35] were prepared as described tances are also similar to values found in other homonu-elsewhere.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Homo- and Hetero-Bimetallic Complexes Containing the Ni(C6F5)2 Moiety – Crystal Structure of [(C6F5)2Ni(μ-SPh)2Pd(dppe)]

Sánchez

Momblona

Sánchez

et al. 1998

Eur. J. Inorg. Chem.

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The compound cis‐[Ni(C6F5)2(PhCN)2] has been used as the starting material for the preparation of the bimetallic complexes [(C6F5)2Ni(μ‐X)2Ni(C6F5)2]2– (X = SCN, OCN, N3), [(C6F5)2Ni(μ‐SCN)2Pd(C6F5)2]2–, [(C6F5)2Ni(μ‐NCS)2Pd‐(dppe)] [dppe = 1,2‐bis(diphenylphosphanyl)ethane], and the trimetallic[(C6F5)2Ni(μ‐NCS)2Pd(μ‐SCN)2Ni(C6F5)2]2–. The mononuclear compounds [(C6F5)2NiLX] (L = PPh3, P(C6H4MeO‐p)3; X = SCN, OCN) are obtained by reaction between [(C6F5)2Ni(&μ‐X)2Ni‐(C6F5)2]2– and L. The treatment of cis‐[Ni(C6F5)2(PhCN)2] with [M(SAr)2(dppe)] leads to the formation of the arylthiolate complexes [(C6F5)2Ni(μ‐SAr)2M(dppe)] (Ar = Ph, C6H4Me‐p, C6H4NO2‐p; M = Ni, Pd, Pt). The X‐ray diffraction study of [(C6F5)2Ni(μ‐SPh)2Pd(dppe)] shows that both metal atoms, Ni and Pd, are coordinated in a slightly distorted square‐planar geometry and the μ‐thiolato groups are in the syn conformation.

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“…The reactions of platinum(II), palladium(II), or nickel(II) salts with organothiol ligands RSH (R = n-alkyl and aryl substituents) in aqueous media were reported to afford intractable amorphous precipitates. [15,16] This observation presents a challenge in obtaining crystals with quality suitable for structural determination by single crystal X-ray crystallography. Herein, we report the synthesis of phase-pure crystalline solid samples of [M(ER) 2 ] 1 complexes (M = Pt, Pd, Ni, E = S or Se, and R = n-alkyl or aryl substituents) in moderate yields, which were obtained by 1) one-pot reactions under solvothermal conditions and/or 2) solvothermal annealing treatment of the respective amorphous solid precipitates obtained under ambient conditions.…”

Section: Solvothermal Synthesismentioning

confidence: 99%

“…Solid-state diffuse re-flectance spectra reveal that the optical band gap E g (eV) of complexes 1, 6, 8, 10 and of 2,7,9,11 are in the range of 2.10-3.00 eV and 2.10-2.63 eV, respectively, and 5 has the lowest E g value (1.72 eV). Heating solid samples of 4 and 13 under solvothermal conditions afforded phase-pure Pd 17 Se 15 and PdS nanocrystals, respectively. Field-effect transistors fabricated with a drop-cast thin film made from Pd 17 Se 15 nanocrystals prior treated with an ethanolic solution of 1-hexadecanethiol displayed ambipolar charge transporting properties with hole and electron mobility being 7 10 À2 cm 2 V À1 s À1 and 6 10 À2 cm 2 V À1 s À1 , respectively.…”

Section: Introductionmentioning

confidence: 99%

Homoleptic Platinum(II) and Palladium(II) Organothiolates and Phenylselenolates: Solvothermal Synthesis, Structural Determination, Optical Properties, and Single‐Source Precursors for PdSe and PdS Nanocrystals

Chui¹,

Low²,

Lu³

et al. 2010

Chemistry An Asian Journal

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Homoleptic d(8)-metal organothiolates and phenylselenolates [M(EC(6)H(5))(2)](infinity) (E=S, M=Pt 1, M=Pd 2, M=Ni 5; E=Se, M=Pt 3, M=Pd 4) were prepared as crystalline solids under solvothermal conditions. Their structures were solved using powder X-ray diffraction data. In each case, the EC(6)H(5) (E=S, Se) ligand binds to two metal ions (M=Pt, Pd, and Ni) to form chain-like structures with planar (in 1) or zig-zag (in 2-5) conformations. The [M(SR)(2)](infinity) complexes (M=Pt, R=4-tert-butylphenyl 6; R=2-naphthyl 8; R=4-nitrophenyl 10 and M=Pd, R=4-tert-butylphenyl 7; R=2-naphthyl 9; R=4-nitrophenyl 11) were prepared under similar solvothermal conditions. Based on the XPS binding energies and elemental analyses, complexes 6-11 have the same [M(SR)(2)](infinity) formulation as 1 and 2. The cyclic complex [Pd(6)(SCH(3))(12)] 12 was prepared as a crystalline solid by solvothermal annealing treatment of the amorphous precipitate. A chain-like polymer structure is proposed for both [Pd(SC(12)H(25))(2)](infinity) 13 and [Pd(SC(16)H(33))(2)](infinity) 14; these polymeric chains self-assemble to give layer-like structures. Solid-state diffuse reflectance spectra reveal that the optical band gap E(g) (eV) of complexes 1, 6, 8, 10 and of 2, 7, 9, 11 are in the range of 2.10-3.00 eV and 2.10-2.63 eV, respectively, and 5 has the lowest E(g) value (1.72 eV). Heating solid samples of 4 and 13 under solvothermal conditions afforded phase-pure Pd(17)Se(15) and PdS nanocrystals, respectively. Field-effect transistors fabricated with a drop-cast thin film made from Pd(17)Se(15) nanocrystals prior treated with an ethanolic solution of 1-hexadecanethiol displayed ambipolar charge transporting properties with hole and electron mobility being 7x10(-2) cm(2) V(-1) s(-1) and 6x10(-2) cm(2) V(-1) s(-1), respectively.

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Some mercaptides and mercaptide complexes of nickel and palladium

Cited by 60 publications

References 9 publications

Active-Site Models for the Nickel–Iron Hydrogenases: Effects of Ligands on Reactivity and Catalytic Properties

Active-Site Models for the Nickel–Iron Hydrogenases: Effects of Ligands on Reactivity and Catalytic Properties

Synthesis of Homo- and Hetero-Bimetallic Complexes Containing the Ni(C6F5)2 Moiety – Crystal Structure of [(C6F5)2Ni(μ-SPh)2Pd(dppe)]

Homoleptic Platinum(II) and Palladium(II) Organothiolates and Phenylselenolates: Solvothermal Synthesis, Structural Determination, Optical Properties, and Single‐Source Precursors for PdSe and PdS Nanocrystals

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