[{Ni2(μ‐CNMe)(CNMe)4(Ph2PCH2PPh2)}2Hg]‐[NiCl4], a Spirocyclic Ni4Hg Cluster with an HgII‐Center

Gong, Jianchun; Huang, Jiaxin; Fanwick, Phillip E.; Kubiak, Clifford P.

doi:10.1002/anie.199003961

Cited by 17 publications

(8 citation statements)

References 15 publications

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“…Selected bond lengths and angles are listed in Table . The most reasonable Ni−Hg separation that can be derived from the data is 2.756(8) Å, which is greater than those reported for complexes believed to contain covalent Ni−Hg bonds, such as [{Ni 2 (μ-CNMe)(CNMe) 4 (dppm) 2 }Hg][NiCl 4 ] [2.617(2)-2.682(2) Å], [Hg{Ni((GePh 3 )(HgGePh 3 )(η 5 -C 5 H 5 )) 2 ] [2.462(3) Å], and [Hg{Ni(η 5 -C 5 H 5 )(PEt 3 ) 2 } 2 ] [2.468(1) Å] . Thus, as with the analogous platinum and palladium complexes, the metal−mercury distance in 11 seems to indicate a weak Ni → Hg interaction.…”

Section: Resultsmentioning

confidence: 80%

Bis{(2-diphenylphosphino)phenyl}mercury: A P-Donor Ligand and Precursor to Mixed Metal−Mercury (d⁸−d¹⁰) Cyclometalated Complexes Containing 2-C₆H₄PPh₂

et al. 2002

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Treatment of HgCl(2) with 2-LiC(6)H(4)PPh(2) gives [Hg(2-C(6)H(4)PPh(2))(2)] (1), whose phosphorus atoms take up oxygen, sulfur, and borane to give the compounds [Hg[2-C(6)H(4)P(X)Ph(2)](2)] [ X = O (3), S (4), and BH(3) (5)], respectively. Compound 1 functions as a bidentate ligand of wide, variable bite angle that can span either cis or trans coordination sites in a planar complex. Representative complexes include [HgX(2) x 1] [X = Cl (6a), Br (6b)], cis-[PtX(2) x 1] [X = Cl (cis-7), Me (9), Ph (10)], and trans-[MX(2) x 1] [X = Cl, M = Pt (trans-7), Pd (8), Ni (11); X = NCS, M = Ni (13)] in which the central metal ions are in either tetrahedral (6a,b) or planar (7-11, 13) coordination. The trans disposition of 1 in complexes trans-7, 8, and 11 imposes close metal-mercury contacts [2.8339(7), 2.8797(8), and 2.756(8) A, respectively] that are suggestive of a donor-acceptor interaction, M --> Hg. Prolonged heating of 1 with [PtCl(2)(cod)] gives the binuclear cyclometalated complex [(eta(2)-2-C(6)H(4)PPh(2))Pt(mu-2-C(6)H(4)PPh(2))(2)HgCl] (14) from which the salt [(eta(2)-2-C(6)H(4)PPh(2))Pt(mu-2-C(6)H(4)PPh(2))(2)Hg]PF(6) (15) is derived by treatment with AgPF(6). In 14 and 15, the mu-C(6)H(4)PPh(2) groups adopt a head-to-tail arrangement, and the Pt-Hg separation in 14, 3.1335(5) A, is in the range expected for a weak metallophilic interaction. A similar arrangement of bridging groups is found in [Cl((n)Bu(3)P)Pd(mu-C(6)H(4)PPh(2))(2)HgCl] (16), which is formed by heating 1 with [PdCl(2)(P(n)()Bu(3))(2)]. Reaction of 1 with [Pd(dba)(2)] [dba = dibenzylideneacetone] at room temperature gives [Pd(1)(2)] (19) which, in air, forms a trigonal planar palladium(0) complex 20 containing bidentate 1 and the monodentate phosphine-phosphine oxide ligand [Hg(2-C(6)H(4)PPh(2))[2-C(6)H(4)P(O)Ph(2)]]. On heating, 19 eliminates Pd and Hg, and the C-C coupled product 2-Ph(2)PC(6)H(4)C(6)H(4)PPh(2)-2 (18) is formed by reductive elimination. In contrast, 1 reacts with platinum(0) complexes to give a bis(aryl)platinum(II) species formulated as [Pt(eta(1)-C-2-C(6)H(4)PPh(2))(eta(2)-2-C(6)H(4)PPh(2))(eta(1)-P-1)]. Crystal data are as follows. Compound 3: monoclinic, P2(1)/n, with a = 11.331(3) A, b = 9.381(2) A, c = 14.516 A, beta = 98.30(2) degrees, and Z = 2. Compound 6b x 2CH(2)Cl(2): triclinic, P macro 1, with a = 12.720(3) A, b = 13.154(3) A, c = 12.724(2) A, alpha = 92.01(2) degrees, beta = 109.19(2) degrees, gamma = 90.82(2) degrees, and Z = 2. Compound trans-7 x 2CH(2)Cl(2): orthorhombic, Pbca, with a = 19.805(3) A, b = 8.532(4) A, c = 23.076(2) A, and Z = 4. Compound 11 x 2CH(2)Cl(2): orthorhombic, Pbca, with a = 19.455(3) A, b = 8.496(5) A, c = 22.858(3) A, and Z = 4. Compound 14: monoclinic, P2(1)/c, with a = 13.150(3) A, b = 12.912(6) A, c = 26.724(2) A, beta = 94.09(1) degrees, and Z = 4. Compound 20 x C(6)H(5)CH(3).0.5CH(2)Cl(2): triclinic, P macro 1, with a = 13.199(1) A, b = 15.273(2) A, c = 17.850(1) A, alpha = 93.830(7), beta = 93.664(6), gamma = 104.378(7) degrees, and Z = 2.

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Section: Resultsmentioning

confidence: 80%

Bis{(2-diphenylphosphino)phenyl}mercury: A P-Donor Ligand and Precursor to Mixed Metal−Mercury (d⁸−d¹⁰) Cyclometalated Complexes Containing 2-C₆H₄PPh₂

et al. 2002

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“…Only a few Ni-Hg complexes have been reported in the Cambridge Structural Database; 60−67 Kubiak has reported a Hg center bound to four Ni centers, albeit in a distorted planar-Hg geometry. 67 The closest structural analogues with respect to the capping μ 4 -Hg environment in 2 have been reported in Au, Au/Pd, and Au/Pt clusters. 68,69 Similarly to 1, samples of 2 in C 6 D 6 were found to undergo H/ D exchange with the solvent, which could be monitored by a decrease of the hydride resonance intensity in the 1 H NMR and an increase in the intensity of the C 6 D 5 H resonance.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Mechanistic Insight into H/D Exchange by a Pentanuclear Ni–H Cluster and Synthesis and Characterization of Structural Analogues of Potential Intermediates

2017

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Experiments to gain mechanistic insight into catalytic H/D exchange of unactivated arenes by [( i Pr 3 P)-Ni] 5 H 6 (1) are described. The reaction order with respect to 1, arene substrate, and added i Pr 3 P were determined, as well as the temperature dependence of reaction rate. Site-selectivity data were obtained by monitoring the reaction of 1 with fluorobenzene and 2-methoxynaphthalene. H/D exchange competition reactions between arenes reacted with 1 were performed. The addition of an excess of Hg to a solution of 1 provided the new heterometallic cluster [( i Pr 3 P)Ni] 5 H 6 (μ 4 -Hg) (2); this species also undergoes H/D exchange with C 6 D 6 , albeit more slowly than 1. Reaction of cluster 1 with TlCp (Cp = C 5 H 5 ) gave (η 5 -Cp)Ni[( i Pr 3 P)Ni] 4 (μ 2 -H) 4 (μ 4 -Tl) (3) with the loss of H 2 . A similar transfer of cyclopentadienyl to Ni occurred when 1 was reacted with MgCp 2 , to give (η 5 -Cp)Ni[( i Pr 3 P)Ni] 4 H 6 (μ 4 -MgCp) (4), but not H 2 loss. Reaction of 1 with cyclopentadiene gave the 5-coordinate hydride complex (η 5 -Cp)Ni[( i Pr 3 P)Ni] 4 (μ 2 -H) 4 (μ 5 -H) (5). The Cp* analogue, (η 5 -Cp*)Ni[( i Pr 3 P)Ni] 4 (μ 2 -H) 4 (μ 5 -H) (6) (where Cp* = C 5 Me 5 ), was synthesized by reacting 1 with LiCp* in THF, or by reaction of 1 with pentamethylcyclopentadiene.

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“…The d 10 -d 10 , dppm bridged dinuclear nickel complex Ni 2 (µ-CNCH 3 )(CNCH 3 ) 2 (µ-dppm) 2 (1) exhibits rich chemistry ranging from simple redox chemistry to transmetalation and multiple bond metathesis. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] Previously, the oxidation of 1 to 1 2+ and several reactions of 1 with electrophiles were reported. [1][2][3][4] The bridging isocyanide of 1 can be alkylated with alkyl halides to form [Ni 2 (µ-CN(R)Me)(CNMe) 2 (µdppm) 2 ] + .…”

Section: Introductionmentioning

confidence: 99%

“…3,4 The bridging isonitrile of 1 is labile and is readily exchanged 2+ , respectively. [8][9][10][11] Prior to the studies presented here, no investigations of the effects of altering the isocyanide ligands have been reported. Similarly, the nature of the mixed valencies in the +1 and +2 states had not been characterized.…”

Section: Introductionmentioning

confidence: 99%

Structural, Spectroscopic, and Electrochemical Studies of the Complexes [Ni₂(μ-CNR)(CNR)₂(μ-dppm)₂]ⁿ⁺(n= 0, 1, 2): Unusual Examples of Nickel(0)−Nickel(I) and Nickel(0)−Nickel(II) Mixed Valency

et al. 2004

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Reaction of Ni(COD)(2) (COD = cyclooctadiene) with dppm (dppm = bis(diphenylphosphino) methane) followed by addition of alkyl or aryl isocyanides yields the class of nickel(0) dimers Ni(2)(mu-CNR)(CNR)(2)(mu-dppm)(2) (R = CH(3) (1), n-C(4)H(9) (2), CH(2)C(6)H(5) (3), i-C(3)H(7) (4), C(6)H(11) (5), t-C(4)H(9) (6), p-IC(6)H(4) (7), 2,6-(CH(3))(2)C(6)H(3) (8)). The cyclic voltammograms of the dimers exhibit two sequential single electron oxidations to the +1 and +2 forms. Specular reflectance infrared spectroelectrochemical (IRSEC) measurements demonstrate reversible interconversions between the neutral Ni(0) dimers and their +1 and +2 forms. Bulk samples of the +2 forms are prepared by chemical oxidation using [FeCp(2)][PF(6)], while the +1 forms are prepared by the comproportionation of neutral and +2 forms. The neutral complexes 6 and 8 were characterized by X-ray diffraction as symmetric, locally tetrahedral binuclear Ni(0) complexes. The +2 forms of these complexes, 6(2+) and 8(2+), have asymmetric structures with one locally square planar and one locally tetrahedral metal center, evidence for a Ni(II)-Ni(0) mixed valence state. The X-ray structural characterization of 6(+) is symmetrical and qualitatively similar to that of the neutral complex 6. The +1 forms all exhibit intense near IR electronic absorptions that are assigned as intervalence charge transfer (IVCT) bands. On the basis of structural, spectroscopic, and electrochemical data, the +1 forms of the complexes, 1(+)-8(+), are assigned as Robin-Day class III, fully delocalized Ni(+0.5)-Ni(+0.5) mixed valence complexes.

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[{Ni₂(μ‐CNMe)(CNMe)₄(Ph₂PCH₂PPh₂)}₂Hg]‐[NiCl₄], a Spirocyclic Ni₄Hg Cluster with an Hg^II‐Center

Cited by 17 publications

References 15 publications

Bis{(2-diphenylphosphino)phenyl}mercury: A P-Donor Ligand and Precursor to Mixed Metal−Mercury (d⁸−d¹⁰) Cyclometalated Complexes Containing 2-C₆H₄PPh₂

Bis{(2-diphenylphosphino)phenyl}mercury: A P-Donor Ligand and Precursor to Mixed Metal−Mercury (d⁸−d¹⁰) Cyclometalated Complexes Containing 2-C₆H₄PPh₂

Mechanistic Insight into H/D Exchange by a Pentanuclear Ni–H Cluster and Synthesis and Characterization of Structural Analogues of Potential Intermediates

Structural, Spectroscopic, and Electrochemical Studies of the Complexes [Ni₂(μ-CNR)(CNR)₂(μ-dppm)₂]ⁿ⁺(n= 0, 1, 2): Unusual Examples of Nickel(0)−Nickel(I) and Nickel(0)−Nickel(II) Mixed Valency

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[{Ni2(μ‐CNMe)(CNMe)4(Ph2PCH2PPh2)}2Hg]‐[NiCl4], a Spirocyclic Ni4Hg Cluster with an HgII‐Center

Cited by 17 publications

References 15 publications

Bis{(2-diphenylphosphino)phenyl}mercury: A P-Donor Ligand and Precursor to Mixed Metal−Mercury (d8−d10) Cyclometalated Complexes Containing 2-C6H4PPh2

Bis{(2-diphenylphosphino)phenyl}mercury: A P-Donor Ligand and Precursor to Mixed Metal−Mercury (d8−d10) Cyclometalated Complexes Containing 2-C6H4PPh2

Mechanistic Insight into H/D Exchange by a Pentanuclear Ni–H Cluster and Synthesis and Characterization of Structural Analogues of Potential Intermediates

Structural, Spectroscopic, and Electrochemical Studies of the Complexes [Ni2(μ-CNR)(CNR)2(μ-dppm)2]n+(n= 0, 1, 2): Unusual Examples of Nickel(0)−Nickel(I) and Nickel(0)−Nickel(II) Mixed Valency

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[{Ni₂(μ‐CNMe)(CNMe)₄(Ph₂PCH₂PPh₂)}₂Hg]‐[NiCl₄], a Spirocyclic Ni₄Hg Cluster with an Hg^II‐Center

Bis{(2-diphenylphosphino)phenyl}mercury: A P-Donor Ligand and Precursor to Mixed Metal−Mercury (d⁸−d¹⁰) Cyclometalated Complexes Containing 2-C₆H₄PPh₂

Bis{(2-diphenylphosphino)phenyl}mercury: A P-Donor Ligand and Precursor to Mixed Metal−Mercury (d⁸−d¹⁰) Cyclometalated Complexes Containing 2-C₆H₄PPh₂

Structural, Spectroscopic, and Electrochemical Studies of the Complexes [Ni₂(μ-CNR)(CNR)₂(μ-dppm)₂]ⁿ⁺(n= 0, 1, 2): Unusual Examples of Nickel(0)−Nickel(I) and Nickel(0)−Nickel(II) Mixed Valency