Syntheses and properties of molecular nickel(II) hydride, methyl, and nickel(I) complexes supported by trimethylphosphane and (2-diphenylphosphanyl)thiophenolato and -naphtholato ligands

Kraikivskii, P. B.; Frey, Markus; Bennour, Hamdi A. M.; Gembus, Armin; Hauptmann, R.; Svoboda, Ingrid; Fueß, H.; Saraev, V. V.; Klein, Hans‐Friedrich

doi:10.1016/j.jorganchem.2009.01.023

Cited by 22 publications

(15 citation statements)

References 67 publications

(79 reference statements)

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“…6c,22a,46 Oxidative addition of S-H bonds to nickel have precedent with chelating substrates. 47 The potential use of this reaction for catalytic S-C bond formation 48 is under investigation.…”

Section: Dalton Transactions Papermentioning

confidence: 99%

Synthesis and chemistry of bis(triisopropylphosphine) nickel(i) and nickel(0) precursors

et al. 2013

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High yield syntheses of ((i)Pr(3)P)(2)NiX (3a-c), (where X = Cl, Br, I) were established by comproportionation of ((i)Pr(3)P)(2)NiX(2) (1a-c) with ((i)Pr(3)P)(2)Ni(η(2)-C(2)H(4)) (2). Reaction of 1a with either NaH or LiHBEt(3) provided ((i)Pr(3)P)(2)NiHCl (4), along with 3a as a side-product. Reduction of ((i)Pr(3)P)(2)NiCl (3a-c) with Mg in presence of nitrogen saturated THF solutions provided the dinitrogen complex [((i)Pr(3)P)(2)Ni](2)(μ-η(1):η(1)-N(2)) (5). In aromatic solvents such as benzene and toluene a thermal equilibrium exists between 5 and the previously reported monophosphine solvent adducts ((i)Pr(3)P)Ni(η(6)-arene) (6a,b). Reaction of 5 with carbon dioxide provided ((i)Pr(3)P)(2)Ni(η(2)-CO(2)) (7). Thermolysis of 9 at 60 °C provided a mixture of products that included the reduction product ((i)Pr(3)P)(2)Ni(CO)(2) (8) along with (i)Pr(3)P=O, as identified by NMR spectroscopy. Complex 8 was also prepared in high yield from the reaction of 5 with CO. Reaction of 5 with CS(2) gave the dimeric carbon disulfide complex [((i)Pr(3)P)Ni(μ-η(1):η(2)-CS(2))](2) (9). Diphenylphosphine reacts with 5 to form the dinuclear Ni(I) complex [((i)Pr(3)P)Ni(μ(2)-PPh(2))](2) (10). Complex 5 reacts with PhSH to form ((i)Pr(3)P)(2)Ni(SPh)(H) (11), which slowly loses H(2) and (i)Pr(3)P to form the dimeric Ni(I) complex [((i)Pr(3)P)Ni(μ(2)-SPh)](2) (12) at room temperature. Complex 12 was also accessed by salt metathesis from the reaction of ((i)Pr(3)P)(2)NiCl (3a) with PhSLi, which demonstrates the utility of 3a as a Ni(I) precursor. With the exception of 6a,b, all compounds were structurally characterized by single-crystal X-ray crystallography.

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Section: Dalton Transactions Papermentioning

confidence: 99%

Synthesis and chemistry of bis(triisopropylphosphine) nickel(i) and nickel(0) precursors

et al. 2013

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“…In mass spectra recorded for ethyl complexes of nickel under comparable conditions, the molecular ion peak intensities do not exceed 5% [24]. A comparative anal ysis allows one to state that the π allyl group in com plex I is coordinated to the metal atom more strongly than in other organometallic nickel complexes and is less prone to dissociation under electron impact.…”

Section: Resultsmentioning

confidence: 92%

“…The yield of complex II was 1.99 g 1H, CH(30)), 1.11 (m, 3H, CH 3 31), 1.16m, 3H, CH 3 32). 13 C NMR (125 MHz, THF d 8 , 297 K, δ, ppm): 158.17 (C(1)), 123.02 (C(3)), 123.53 (C(4)), 123.43 (C(5)), 146.54 (C(6)), 69.56 (C(7)), 184.13 (C(8)), 147.17 (C(9)), 139.71 (C(10)), 124.17 (C(11)), 127.13 (C(12)), 124.43 (C(13)), 140.20 (C(14)), 53.97 (C(15)), 106.7 (C(16)), 50.71 (C(17)), 28.45 (C(18)), 26.10 (C(19)), 26.26 (C(20)), 28.28 (C(21)), 24.89, 25.15 (C(22), C(23)), 124.18 (C(24)), 140.88 (C(25)), 19.26 (C(26)), 29.22 (C(27)), 23.78 (C(28)), 24.00 (C(29)), 29.42 (C(30)), 24.28 (C(31)), 24.62 (C(32)). (13) A solution of complex I in THF d 8 was kept in a sealed NMR tube at 25°C while monitoring its trans formation by the DEPT 135 13 C NMR technique.…”

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confidence: 99%

Nickel(I) complex as the final product of the sequence of spontaneous transformations in the system Ni(allyl)2-(2,6-diisopropylphenyl)diazabutadiene

et al. 2012

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A survey of the literature data on transition metal complexes with allyl ligands since the synthesis of their first representatives [1, 2] till now [3][4][5][6] has revealed that the π allyl structure of transition metal complexes takes an important part in catalytic reactions. This relates to π allyl fragments both originally present in a transition metal complex or formed immediately in its coordination sphere during reactions of complexes with olefins at a metal complex catalyst. As a rule, a π allyl complex in catalytic systems is stabilized by various organometallic ligands. A catalytic system based on nickel and palladium diimine complexes has been proposed in [7,8]. An undoubted advantage of such systems is that lower olefins can be transformed into linear polymers with a considerable α form con tent. This type of catalytic systems holds promise as precursors of cationic or electrically neutral allyl nickel and palladium complexes with various diimine ligands including the diazabutadiene fragment [8]. Although such catalytic systems are currently under intensive study, a question is still open as to whether N containing ligands themselves can be transformed in organometallic complexes. As a result, almost all the mechanisms proposed in the literature for the cat alytic cycle ignore possible changes in the nature of the metal-ligand bond and in the structure of the diimine ligand itself [9][10][11][12][13][14][15]. One can state that this ligand is most often regarded as an unchangeable entity involved in the catalytic cycle as a "guest" that can either be coordinated to the metal center or quit its coordination sphere intact. Thus, possible transfor mations of the ligand itself are usually left out. In addi tion, the catalytic cycle mechanisms considered in the overwhelming majority of relevant studies are based on nickel(0) and nickel(2) complexes. The Ni +2 form is regarded as the second most stable species inferior only to colloidal nickel [9, 13-15]. However, some authors do note the formation of nickel(I) complexes from both nickel(II) complexes with allyl [6] and diimine ligands [10,11].Furthermore, despite much research dealing with allyl complexes of transition metals, the literature data on nickel allyl systems are very scarce because the attention of researchers is mainly focused on allyl complexes of palladium [16]. Obviously, this is due to both the relatively low stability of allyl complexes of nickel and the limited scope of their study by the most commonly used method (NMR spectroscopy) [17].In this work, we studied in detail complexation between bisallylnickel(II) and bis(2,6 diisopropyl phenyl)diazabutadiene (DAB) by NMR, EPR, and IR spectroscopy; DAB is an efficient, abundant, and syn thetically accessible diimine ligand. EXPERIMENTAL All manipulations were performed using standard Schlenk ware with an argon-vacuum double manifold glass line. Solvents and volatile components were admit ted into the systems by recondensation; solid components were added from evacuated tubes fused to the sy...

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“…In paper [20] comparable conditions were used for recording mass spectra of nickel ethyl complexes, though the intensities of the molecular ion signals were less 5%. The comparative analysis of p-allyl group in 1 and that of other organometallic nickel complexes allows us to say that the former has stronger bonding with the metal and it is less susceptible to dissociation by impact ionization.…”

Section: Resultsmentioning

confidence: 99%

Formation of the paramagletic Ni(I) π-allyl complex in the Ni(allyl)2 – (2,6-diisopropylphenyl)diazabutadiene system

Kraikivskii

Saraev

Bocharova

et al. 2011

Journal of Organometallic Chemistry

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Syntheses and properties of molecular nickel(II) hydride, methyl, and nickel(I) complexes supported by trimethylphosphane and (2-diphenylphosphanyl)thiophenolato and -naphtholato ligands

Cited by 22 publications

References 67 publications

Synthesis and chemistry of bis(triisopropylphosphine) nickel(i) and nickel(0) precursors

Synthesis and chemistry of bis(triisopropylphosphine) nickel(i) and nickel(0) precursors

Nickel(I) complex as the final product of the sequence of spontaneous transformations in the system Ni(allyl)2-(2,6-diisopropylphenyl)diazabutadiene

Formation of the paramagletic Ni(I) π-allyl complex in the Ni(allyl)2 – (2,6-diisopropylphenyl)diazabutadiene system

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