Monomeric Nickel(II) Amido Complexes. Synthesis, Reactivity, and Dynamics

VanderLende, Daniel D.; Abboud, Khalil A.; Boncella, James M.

doi:10.1021/ic00125a035

Cited by 50 publications

(44 citation statements)

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“…The Ni-N(terminal) distance found in [ i Pr-PNP]Ni(NHPh) is comparable to other terminal anilidonickel complexes such as (g 5 -C 5 Me 5 )Ni(NH-p-tolyl)(PEt 3 ) (1.903(5) A ˚)21 and trans-Ni(NHPh)(mesityl)(PMe 3 ) 2 (1.932(3) A ˚). 31 The N(2)-C(25) distance of 1.351(5) A ˚is relatively short as compared to the typical N-C sp2 bond length of ca. 1.40 A ˚, indicating partial delocalization of the nitrogen lone pair into the phenyl ring.…”

Section: Resultsmentioning

confidence: 98%

“…The assignment of the carbon atoms is based on DEPT 13 C NMR spectroscopy. 31 38 were prepared according to the procedures reported previously. All other chemicals were obtained from commercial vendors and used as received.…”

Section: General Proceduresmentioning

confidence: 99%

“…1 H NMR (500 MHz, C 6 D 6 ) d 8.08 (m, 8, Ar), 7.40 (m, 2, Ar), 7.06 (m, 14, Ar), 6.79 (t, 2, Ar), 6.35 (t, 2, Ar), 0.91 (s, 9, NC(CH 3 ) 3 ), −0.70 (t, 1, J HP = 8.5, NH). 31…”

Section: Synthesis Of [Ph-pnp]ni(nh T Bu)mentioning

confidence: 99%

“…CHMe 2 ), 1.35 (dd, 12, CHMe 2 ), −1.18 (s, 1, NiNHPh) 31. P{ 1 H} NMR (C 6 D 6 , 202.3 MHz) d 29.25.…”

mentioning

confidence: 99%

“…H NMR (C 6 D 6 , 500 MHz) d 7.54 (d, 2, Ar), 7.50 (d, 2, Ar), 7.28 (t, 2, Ar), 7.03 (m, 2, Ar), 6.9 (t, 2, Ar), 6.68 (t, 1, Ar), 6.44 (t, 2, Ar), 2.50 (m, 4, PCH), 2.05 (m, 4, Cy), 1.95 (q, 4, Cy), 1.82 (m, 4, Cy), 1.60 (m, 12, Cy), 1.48 (m, 4, Cy), 1.20 (q, 4, Cy), 1.03 (q, 8, Cy) 31. P{ 1 H} NMR (THF, 80.9 MHz) d 20.92 31. P{ 1 H} NMR (C 6 D 6 , 202.3 MHz) d 21.00.…”

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confidence: 99%

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Terminal nickel(ii) amide, alkoxide, and thiolate complexes containing amido diphosphine ligands of the type [N(o-C6H4PR2)2]− (R = Ph, iPr, Cy)

et al. 2008

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A series of nickel(ii) complexes of the type [R-PNP]Ni(ER') ([R-PNP](-) = [N(o-C(6)H(4)PR(2))(2)](-); R = Ph, (i)Pr, Cy; E = NH, O, S; R' = Ph, (t)Bu) featuring unsupported, covalently bound pi-donor ligands have been prepared and characterized. The metathetical reactions of [R-PNP]NiCl (R = Ph, (i)Pr, Cy) with LiNHPh, NaOPh, or NaSPh, respectively, produced the corresponding anilide [R-PNP]Ni(NHPh), phenolate [R-PNP]Ni(OPh), and thiophenolate [R-PNP]Ni(SPh) derivatives. Treatment of [Ph-PNP]NiCl with either LiNH(t)Bu or NaO(t)Bu generated tert-butyl amide [Ph-PNP]Ni(NH(t)Bu) and tert-butoxide [Ph-PNP]Ni(O(t)Bu), respectively. In contrast, attempts to prepare analogous tert-butyl amide and tert-butoxide complexes of [(i)Pr-PNP](-) or [Cy-PNP](-) were not successful. Protonolysis studies of these nickel(ii)-heteroatom complexes revealed the basic reactivity of these pi-donor ligands. The basicity follows the order NH(t)Bu > O(t)Bu > NHPh > OPh > SPh. In addition to solution NMR spectroscopic data for all new compounds, X-ray structures of [(i)Pr-PNP]Ni(NHPh) and [(i)Pr-PNP]Ni(OPh) are presented.

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Section: Resultsmentioning

confidence: 98%

Section: General Proceduresmentioning

confidence: 99%

“…1 H NMR (500 MHz, C 6 D 6 ) d 8.08 (m, 8, Ar), 7.40 (m, 2, Ar), 7.06 (m, 14, Ar), 6.79 (t, 2, Ar), 6.35 (t, 2, Ar), 0.91 (s, 9, NC(CH 3 ) 3 ), −0.70 (t, 1, J HP = 8.5, NH). 31…”

Section: Synthesis Of [Ph-pnp]ni(nh T Bu)mentioning

confidence: 99%

“…CHMe 2 ), 1.35 (dd, 12, CHMe 2 ), −1.18 (s, 1, NiNHPh) 31. P{ 1 H} NMR (C 6 D 6 , 202.3 MHz) d 29.25.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

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Terminal nickel(ii) amide, alkoxide, and thiolate complexes containing amido diphosphine ligands of the type [N(o-C6H4PR2)2]− (R = Ph, iPr, Cy)

et al. 2008

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Synthesis and Crystal Structures of Monomeric Diamidonickel(II) Complexes

Lee

Peng

Kui

et al. 2000

Eur. J. Inorg. Chem.

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The thermally stable nickel(II) diamides [NiL2] [L = −N(SiMe3)(8‐C9H6N) (1), −N(SitBuMe2)(8‐C9H6N) (2)] have been synthesized from the reaction of NiCl2 with the appropriate lithium amide. X‐ray crystallography revealed that the amido ligands bind in a chelating manner, forming a distorted tetrahedral environment around the nickel center. Complexes 1 and 2 have magnetic moments of 3.05 and 2.74 μB, respectively, which indicate a d8 electronic configuration with two unpaired electrons.

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Reactivity of Triosmium Carbonyl Clusters with 1,8-Diaminonaphthalene − Synthesis and Structural Characterization of Amido, Diamido, andC-Metalated Trinuclear Derivatives

Cabeza¹,

Nöth²,

Rosales-Hoz³

et al. 2000

Eur. J. Inorg. Chem.

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The compounds [Os3(CO)12] and [Os3(μ‐H)2(CO)10] do not react with 1,8‐diaminonaphthalene (H2dan) under thermal conditions (110 °C, 30 min). However, [Os3(CO)10(MeCN)2] reacts with H2dan (THF, reflux temperature) to give two isomers of [Os3(μ‐H)(μ‐Hdan)(CO)9] (1 and 2). In toluene at reflux temperature, these reagents afford [Os3(μ‐dan)(CO)10] (3). Compound 2 can be converted into 3 under thermal conditions, but no interconversion between 1 and 2 has been observed. The three compounds have been characterized by X‐ray diffraction methods. Compound 1 arises from the C‐metalation of H2dan in a position adjacent to an NH2 group; this generates a hydride and a ligand that interacts with the three metal atoms through one of the NH2 groups, through the metalated carbon atom (which spans an Os−Os edge), and through one of the C=C bonds of the metalated ring. In compound 2, the hydride arises from the oxidative addition of an N−H bond of H2dan; the resulting ligand interacts with two of the three metal atoms through the amido NH fragment (bridging position) and through the remaining NH2 group. Compound 3 is derived from the transformation of both NH2 groups of H2dan into amido NH groups and consists of a 50‐electron trinuclear cluster with the longest edge doubly‐bridged by both amido groups.

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Monomeric Nickel(II) Amido Complexes. Synthesis, Reactivity, and Dynamics

Cited by 50 publications

References 0 publications

Terminal nickel(ii) amide, alkoxide, and thiolate complexes containing amido diphosphine ligands of the type [N(o-C6H4PR2)2]− (R = Ph, iPr, Cy)

Terminal nickel(ii) amide, alkoxide, and thiolate complexes containing amido diphosphine ligands of the type [N(o-C6H4PR2)2]− (R = Ph, iPr, Cy)

Synthesis and Crystal Structures of Monomeric Diamidonickel(II) Complexes

Reactivity of Triosmium Carbonyl Clusters with 1,8-Diaminonaphthalene − Synthesis and Structural Characterization of Amido, Diamido, andC-Metalated Trinuclear Derivatives

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